TW202319250A - Articles having polymer film layers - Google Patents

Articles having polymer film layers Download PDF

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TW202319250A
TW202319250A TW111133737A TW111133737A TW202319250A TW 202319250 A TW202319250 A TW 202319250A TW 111133737 A TW111133737 A TW 111133737A TW 111133737 A TW111133737 A TW 111133737A TW 202319250 A TW202319250 A TW 202319250A
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polymer film
film layer
polymer
article
amine
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科斯坦蒂諾斯 庫爾塔基斯
班傑明 薩姆森
丹尼斯 沃爾斯
能 肖
磊 張
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美商杜邦電子股份有限公司
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1075—Partially aromatic polyimides
    • C08G73/1082—Partially aromatic polyimides wholly aromatic in the tetracarboxylic moiety
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    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
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    • B32—LAYERED PRODUCTS
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    • B32B27/00—Layered products comprising a layer of synthetic resin
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    • B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
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    • B32—LAYERED PRODUCTS
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    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
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    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
    • B32B3/02—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by features of form at particular places, e.g. in edge regions
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    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/005—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
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    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B9/045—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
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    • B32B2255/00—Coating on the layer surface
    • B32B2255/20—Inorganic coating
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    • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/10—Properties of the layers or laminate having particular acoustical properties
    • B32B2307/102—Insulating
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    • B32—LAYERED PRODUCTS
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    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/414—Translucent
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    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/558—Impact strength, toughness
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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Laminated Bodies (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)
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Abstract

In a first aspect, an article includes a first polymer film layer and a second polymer film layer. The first polymer film layer includes a first polymer including a first imide group. The second polymer film layer includes a second polymer including a second imide group.

Description

具有聚合物膜層的物品 Items with polymer coatings

本揭露之領域係具有聚合物膜層的製品。 The field of the disclosure is articles having polymeric film layers.

具有聚合物膜層的製品用於利用聚合物可以提供的寬範圍的機械、電、光學和其他特性的多種應用中。無機(例如，陶瓷和玻璃)層壓產品長期以來被用於多種應用，如用於建築物、車輛和人員的裝甲，以及用於透明應用的安全玻璃。除了用於擋風玻璃的眾所周知的、日用汽車安全玻璃外，層壓玻璃還被用作火車、飛機、船舶和幾乎所有其他運輸方式的窗。安全玻璃的特徵在於高的抗衝擊性和抗穿透性並且在破碎時不散落玻璃碎片和碎屑。 Articles having polymeric film layers are used in a variety of applications that take advantage of the wide range of mechanical, electrical, optical and other properties that polymers can provide. Inorganic (eg, ceramic and glass) laminates have long been used in applications such as armor for buildings, vehicles and personnel, and safety glass for transparent applications. In addition to the well-known, everyday automotive safety glass used for windshields, laminated glass is also used as windows in trains, airplanes, ships and virtually every other mode of transportation. Safety glass is characterized by high impact and penetration resistance and does not scatter glass shards and debris when broken.

安全玻璃典型地由與聚合物膜或片的中間層黏合在一起的兩個玻璃片或板的夾層組成，該中間層被置於該兩個玻璃片之間。一個或兩個玻璃片可以用光學透明的剛性聚合物片，如聚碳酸酯材料片來代替。安全玻璃已經進一步發展到包括與聚合物膜或片的中間層黏合在一起的多層玻璃和聚合物片。 Safety glass typically consists of a sandwich of two glass sheets or panels bonded together with an interlayer of polymer film or sheet placed between the two glass sheets. One or both glass sheets may be replaced by sheets of optically transparent rigid polymer, such as polycarbonate material. Safety glass has been further developed to include multiple layers of glass and polymer sheets bonded together with an intermediate layer of polymer film or sheet.

中間層典型地是相對厚的聚合物片，其表現出韌性和黏合性以在裂紋或碰撞的情況下提供對玻璃的黏附。一般來說，希望該等聚合物中間層具有以下特性的組合，包括非常高的光學清晰度、低霧度、高抗衝擊性、高抗穿透性、優異的耐紫外光性、良好的長期熱穩定性、對玻璃和其他剛性聚合物片的優異黏 附、低紫外光透射率、低吸濕性、高防潮性、以及優異的長期耐候性、以及其他要求。 The interlayer is typically a relatively thick sheet of polymer that exhibits toughness and adhesive properties to provide adhesion to the glass in the event of a crack or impact. In general, it is desirable for such polymeric interlayers to have a combination of properties including very high optical clarity, low haze, high impact resistance, high penetration resistance, excellent UV resistance, good long-term Thermal stability, excellent adhesion to glass and other rigid polymer sheets Attachment, low UV transmittance, low moisture absorption, high moisture resistance, and excellent long-term weather resistance, and other requirements.

最近的趨勢係在住宅和辦公建築物(structure)的建設中使用玻璃層壓產品。隨著設計者將更多的玻璃表面結合到建築物中，建築玻璃的使用多年來已經迅速擴大。抗威脅性(Threat resistance)已經成為建築玻璃層壓產品的日益增長的要求。該等較新的產品被設計用來抵抗自然和人為的災害。該等需求的實例包括最近開發的抗颶風玻璃(現在在易受颶風影響的地區被強制)、防盜玻璃製品、以及被設計用來保護建築物及其居住者的最近的防爆玻璃層壓產品。該等產品中的一些具有足夠大的強度，即使在玻璃層壓物已經被破壞後也能抵抗侵入；例如，當玻璃層壓物受到颶風中可能發生的強力風和飛行碎片的衝擊時，或者當罪犯試圖闖入車輛或建築物而對窗進行重複衝擊時。 A recent trend is the use of glass laminated products in the construction of residential and office structures. The use of architectural glass has expanded rapidly over the years as designers incorporate more glass surfaces into buildings. Threat resistance has become an increasing requirement for architectural glass laminated products. These newer products are designed to resist natural and man-made disasters. Examples of such needs include recently developed hurricane resistant glazing (now mandated in hurricane prone areas), burglar resistant glazing, and more recently blast resistant glass laminates designed to protect buildings and their occupants. Some of these products are sufficiently strong to resist intrusion even after the glass laminate has been damaged; for example, when the glass laminate is impacted by the high winds and flying debris that may occur in a hurricane, or When a criminal tries to break into a vehicle or building and repeatedly strikes the window.

光滑的玻璃表面對於在不使用黏合劑的情況下黏附聚合物層提出挑戰。矽烷化係用於將多種官能基引入到玻璃表面上的眾所周知之方法。例如，可以將具有胺基官能的矽烷偶合劑的塗覆溶液沈積到玻璃基材上並乾燥以去除溶劑，得到具有改性表面能的玻璃表面。 Smooth glass surfaces present challenges for adhering polymer layers without the use of adhesives. Silanization is a well-known method for introducing various functional groups onto glass surfaces. For example, a coating solution of an amine-functional silane coupling agent can be deposited onto a glass substrate and dried to remove solvent, resulting in a glass surface with modified surface energy.

聚醯亞胺膜可以藉由將聚醯胺酸溶液塗覆到已經使用胺基官能的矽烷偶合劑進行官能化的矽基材上而黏附至無機基材，如矽基材(A.V.Patsis and S.Cheng,J Adhesion(1988),25,145-157)。當溶液被施加到經處理的表面時，矽烷偶合劑藉由聚醯胺酸上的接酸和胺基團與矽基材上的矽醇基團之間的相互作用與醯胺酸相互作用。在隨後的固化過程中，聚醯胺酸被轉化為聚醯亞胺。 Polyimide membranes can be adhered to inorganic substrates, such as silicon substrates, by coating a polyamide acid solution onto a silicon substrate that has been functionalized with an amino-functional silane coupling agent (A.V. Patsis and S. . Cheng, J Adhesion (1988), 25, 145-157). When the solution is applied to the treated surface, the silane coupling agent interacts with the amide acid through the interaction between the acid and amine groups on the polyamic acid and the silanol groups on the silicon substrate. During the subsequent curing process, polyamic acid is converted to polyimide.

聚合物膜層還被廣泛用於電路級的電子裝置中，以及用於外部裝置層，如顯示器裝置中。當希望兩個或更多個聚合物層時，可以藉由共擠出聚合 物層、或藉由使用塗覆技術製造具有良好黏附的多層聚合物膜構造。例如，可以將聚醯胺酸、或可溶性聚醯亞胺組成物共擠出並固化以形成多層聚醯亞胺膜，或者可以依次沈積聚醯胺酸、或可溶性聚醯亞胺組成物的連續塗層以形成多層膜。 Polymer film layers are also widely used in electronic devices at the circuit level, as well as in external device layers, such as in display devices. When two or more polymer layers are desired, they can be polymerized by coextrusion layer, or by using coating techniques to create multilayer polymer film constructions with good adhesion. For example, the polyamic acid, or soluble polyimide composition can be coextruded and cured to form a multilayer polyimide film, or the polyamic acid, or soluble polyimide composition can be sequentially deposited in succession. coating to form a multilayer film.

在第一態樣，製品包括第一聚合物膜層和第二聚合物膜層。該第一聚合物膜層包括包含第一醯亞胺基團的第一聚合物。該第二聚合物膜層包括包含第二醯亞胺基團的第二聚合物。在該等層之間的介面處分離第一和第二聚合物膜層以暴露第一聚合物膜層的第一介面表面和第二聚合物膜層的第二介面表面之後： In a first aspect, an article includes a first polymeric film layer and a second polymeric film layer. The first polymer film layer includes a first polymer comprising a first imide group. The second polymer film layer includes a second polymer comprising a second imide group. After separating the first and second polymer film layers at the interface between the layers to expose the first interface surface of the first polymer film layer and the second interface surface of the second polymer film layer:

(a)如使用負二次離子質譜法測量的該第一介面表面處的CN-對C3N-物質的比例相較其在該第一聚合物膜層的本體中的比例高至少10%； (a) the ratio of CN - to C 3 N - species at the surface of the first interface as measured using negative secondary ion mass spectrometry is at least 10% higher than its proportion in the bulk of the first polymer film layer ;

(b)如使用負二次離子質譜法測量的該第二介面表面處的CN-對C3N-物質的比例相較其在該第二聚合物膜層的本體中的比例高至少10%；或者 (b) the ratio of CN - to C 3 N - species at the surface of the second interface as measured using negative secondary ion mass spectrometry is at least 10% higher than its proportion in the bulk of the second polymer film layer ;or

(c)如使用負二次離子質譜法測量的該第一介面表面處的CN-對C3N-物質的比例相較其在該第一聚合物膜層的本體中的比例高至少10%，並且如使用負二次離子質譜法測量的該第二介面表面處的CN-與C3N-物質的比例相較其在該第二聚合物膜層的本體中的比例高至少10%。 (c) the ratio of CN - to C 3 N - species at the surface of the first interface as measured using negative secondary ion mass spectrometry is at least 10% higher than in the bulk of the first polymer film layer , and the ratio of CN - to C 3 N - species at the surface of the second interface as measured using negative secondary ion mass spectrometry is at least 10% higher than its ratio in the bulk of the second polymer film layer.

在第二態樣，抗衝擊製品包括第一態樣的製品。 In a second aspect, the impact resistant article comprises the article of the first aspect.

在第三態樣，抗穿透製品包括第一態樣的製品。 In a third aspect, the penetration resistant article comprises the article of the first aspect.

在第四態樣，減音製品包括第一態樣的製品。 In a fourth aspect, the sound reducing article includes the article of the first aspect.

在第五態樣，金屬包層的層壓物包括第一態樣的製品。 In a fifth aspect, the metal-clad laminate comprises the article of the first aspect.

在第六態樣，描述了一種用於形成製品之方法。該製品包括第一聚合物膜層和第二聚合物膜層，該第一聚合物膜層包括具有第一玻璃化轉變溫度並包括第一醯亞胺基團的第一聚合物，該第二聚合物膜層包括具有第二玻璃化轉變溫度並包括第二醯亞胺基團的第二聚合物，其中該第一玻璃化轉變溫度等於或低於該第二玻璃化轉變溫度。該方法包括： In a sixth aspect, a method for forming an article is described. The article includes a first polymer film layer comprising a first polymer having a first glass transition temperature and comprising a first imide group, and a second polymer film layer, the second polymer film layer comprising The polymer film layer includes a second polymer having a second glass transition temperature and including a second imide group, wherein the first glass transition temperature is equal to or lower than the second glass transition temperature. The method includes:

(a)將胺試劑施加至該第一聚合物膜層的表面、該第二聚合物膜層的表面、或兩者； (a) applying an amine reagent to the surface of the first polymer film layer, the surface of the second polymer film layer, or both;

(b)使該等聚合物膜層接觸，使得具有胺試劑的表面在該等聚合物膜層之間的介面處；以及 (b) contacting the polymer film layers such that the surface with the amine reagent is at the interface between the polymer film layers; and

(c)向該製品施加熱量和壓力。 (c) applying heat and pressure to the article.

前面的一般性說明和以下詳細說明僅是示例性的和解釋性的，並且不限制如所附申請專利範圍所限定的本發明。 The foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention, as defined by the claims of the appended applications.

在第一態樣，製品包括第一聚合物膜層和第二聚合物膜層。第一聚合物膜層包括包含第一醯亞胺基團的第一聚合物。第二聚合物膜層包括包含第二醯亞胺基團的第二聚合物。在該等層之間的介面處分離第一和第二聚合物膜層以暴露第一聚合物膜層的第一介面表面和第二聚合物膜層的第二介面表面之後： In a first aspect, an article includes a first polymeric film layer and a second polymeric film layer. The first polymer film layer includes a first polymer including a first imide group. The second polymer film layer includes a second polymer comprising a second imide group. After separating the first and second polymer film layers at the interface between the layers to expose the first interface surface of the first polymer film layer and the second interface surface of the second polymer film layer:

(a)如使用負二次離子質譜法測量的第一介面表面處的CN-對C3N-物質的比例相較其在第一聚合物膜層的本體中的比例高至少10%； (a) the proportion of CN - to C 3 N - species at the surface of the first interface as measured using negative secondary ion mass spectrometry is at least 10% higher than its proportion in the bulk of the first polymer film layer;

(b)如使用負二次離子質譜法測量的第二介面表面處的CN-對C3N-物質的比例相較其在第二聚合物膜層的本體中的比例高至少10%；或者 or _ _

(c)如使用負二次離子質譜法測量的第一介面表面處的CN-對C3N-物質的比例相較其在第一聚合物膜層的本體中的比例高至少10%，並且如使用負二次離子質譜法測量的第二介面表面處的CN-對C3N-物質的比例相較其在第二聚合物膜層的本體中的比例高至少10%。 (c) the proportion of CN - to C 3 N - species at the surface of the first interface as measured using negative secondary ion mass spectrometry is at least 10% higher than its proportion in the bulk of the first polymer film layer, and The ratio of CN − to C 3 N − species at the surface of the second interface as measured using negative secondary ion mass spectrometry is at least 10% higher than its ratio in the bulk of the second polymer film layer.

在第一態樣的一個實施方式中，包括醯亞胺基團的第一和第二聚合物各自單獨地選自由以下組成之群組：聚醯亞胺、聚(醯胺-醯亞胺)、聚(醚-醯亞胺)、聚(酯-醯亞胺)、包括醯胺、酯或醚基團的共聚物、及其混合物。在具體實施方式中，聚醯亞胺衍生自二酐、氟化的芳香族二胺和脂肪族二胺。在更具體的實施方式中，二酐包括脂環族二酐。 In one embodiment of the first aspect, the first and second polymers comprising imide groups are each independently selected from the group consisting of polyimides, poly(amide-imides) , poly(ether-imides), poly(ester-imides), copolymers comprising amide, ester or ether groups, and mixtures thereof. In specific embodiments, the polyimides are derived from dianhydrides, fluorinated aromatic diamines, and aliphatic diamines. In a more specific embodiment, the dianhydride comprises a cycloaliphatic dianhydride.

在第一態樣的另一實施方式中，(a)第一聚合物膜層具有300℃或更低的Tg；(b)第二聚合物膜層具有300℃或更低的Tg；或者(c)第一和第二聚合物膜層兩者都具有300℃或更低的Tg。 In another embodiment of the first aspect, (a) the first polymer film layer has a Tg of 300°C or less; (b) the second polymer film layer has a Tg of 300°C or less; Or (c) both the first and second polymer film layers have a Tg of 300°C or less.

在第一態樣的還另一實施方式中，當使用由ASTM E313描述的程序在25μm的厚度下測量時，製品具有1.25或更小的b*和2.25或更小的黃度指數。 In yet another embodiment of the first aspect, the article has a b* of 1.25 or less and a yellowness index of 2.25 or less when measured at a thickness of 25 μm using the procedure described by ASTM E313.

在第一態樣的又另一實施方式中，當在25μm的厚度下測量時，製品具有15%或更小的霧度和93或更大的L*。 In yet another embodiment of the first aspect, the article has a haze of 15% or less and an L* of 93 or greater when measured at a thickness of 25 μm.

在第一態樣的還又另一實施方式中，製品進一步包括在與第二聚合物膜層相反的一側上與第一聚合物膜層接觸的無機基材。 In yet another embodiment of the first aspect, the article further includes an inorganic substrate in contact with the first polymer film layer on a side opposite the second polymer film layer.

在第二態樣，抗衝擊製品包括第一態樣的製品。 In a second aspect, the impact resistant article comprises the article of the first aspect.

在第三態樣，抗穿透製品包括第一態樣的製品。 In a third aspect, the penetration resistant article comprises the article of the first aspect.

在第四態樣，減音製品包括第一態樣的製品。 In a fourth aspect, the sound reducing article includes the article of the first aspect.

在第五態樣，金屬包層的層壓物包括第一態樣的製品。 In a fifth aspect, the metal-clad laminate comprises the article of the first aspect.

在第六態樣，描述了一種用於形成製品之方法。製品包括第一聚合物膜層和第二聚合物膜層，該第一聚合物膜層包括具有第一玻璃化轉變溫度並包括第一醯亞胺基團的第一聚合物，該第二聚合物膜層包括具有第二玻璃化轉變溫度並包括第二醯亞胺基團的第二聚合物，其中第一玻璃化轉變溫度等於或低於第二玻璃化轉變溫度。該方法包括： In a sixth aspect, a method for forming an article is described. The article comprises a first polymer film layer comprising a first polymer having a first glass transition temperature and comprising a first imide group and a second polymer film layer, the second polymer film layer comprising The physical film layer includes a second polymer having a second glass transition temperature and including a second imide group, wherein the first glass transition temperature is equal to or lower than the second glass transition temperature. The method includes:

(a)將胺試劑施加至第一聚合物膜層的表面、第二聚合物膜層的表面、或兩者； (a) applying an amine reagent to the surface of the first polymeric film layer, the surface of the second polymeric film layer, or both;

(b)使該等聚合物膜層接觸，使得具有胺試劑的表面在該等聚合物膜層之間的介面處；以及 (b) contacting the polymer film layers such that the surface with the amine reagent is at the interface between the polymer film layers; and

(c)向製品施加熱量和壓力。 (c) Applying heat and pressure to the article.

在第六態樣的一個實施方式中，胺試劑選自由一級胺、二級胺、或其混合物組成之群組。 In one embodiment of the sixth aspect, the amine reagent is selected from the group consisting of primary amines, secondary amines, or mixtures thereof.

在第六態樣的另一實施方式中，胺試劑包括多胺。 In another embodiment of the sixth aspect, the amine reagent includes a polyamine.

在第六態樣的還另一實施方式中，胺試劑包括金屬醇鹽，該金屬醇鹽包括水解的低聚物。 In yet another embodiment of the sixth aspect, the amine reagent comprises a metal alkoxide comprising a hydrolyzed oligomer.

在第六態樣的又另一實施方式中，施加至第一聚合物膜層的表面的胺試劑與施加至第二聚合物膜層的表面的胺試劑相同或不同。 In yet another embodiment of the sixth aspect, the amine reagent applied to the surface of the first polymer film layer is the same or different than the amine reagent applied to the surface of the second polymer film layer.

在第六態樣的還又另一實施方式中，熱量係在第一聚合物的玻璃化轉變溫度之低20度至高50度範圍內的溫度。 In yet another embodiment of the sixth aspect, the heat is at a temperature ranging from 20 degrees below to 50 degrees above the glass transition temperature of the first polymer.

在第六態樣的另外的實施方式中，胺試劑包括已被鈍化並且可以藉由施加熱量而被熱活化的胺基團。在具體實施方式中，已被鈍化的胺基團在活化後還可以使第一聚合物、第二聚合物、或兩者交聯。 In further embodiments of the sixth aspect, the amine reagent includes an amine group that has been deactivated and can be thermally activated by the application of heat. In specific embodiments, the amine groups that have been deactivated can also crosslink the first polymer, the second polymer, or both after activation.

在第六態樣的還另外的實施方式中，在將胺試劑施加至一個或兩個聚合物膜層的表面之前，一個或兩個聚合物膜層的表面經歷電暈處理(corona treatment)或電漿處理(plasma treatment)。 In still other embodiments of the sixth aspect, prior to applying the amine reagent to the surfaces of the one or both polymeric film layers, the surface of the one or both polymeric film layers undergoes corona treatment or Plasma treatment.

在第六態樣的又另外的實施方式中，製品進一步包括在與第二聚合物膜層相反的一側上與第一聚合物膜層接觸的無機基材。在該方法的步驟(a)期間，還將胺試劑施加至第一聚合物膜層的另一表面、無機基材的表面、或兩者。在該方法的步驟(b)期間，使第一聚合物膜層與無機基材接觸，使得具有胺試劑的表面位於第一聚合物膜層與無機基材之間的介面處。 In still further embodiments of the sixth aspect, the article further includes an inorganic substrate in contact with the first polymer film layer on a side opposite the second polymer film layer. During step (a) of the method, an amine reagent is also applied to the other surface of the first polymeric film layer, the surface of the inorganic substrate, or both. During step (b) of the method, the first polymeric film layer is contacted with the inorganic substrate such that the surface with the amine reagent is at the interface between the first polymeric film layer and the inorganic substrate.

上文已經描述了許多態樣和實施方式，並且該等態樣和實施方式僅是示例性的而非限制性的。在閱讀本說明書後，熟悉該項技術者將理解的是，在不背離本發明之範圍的情況下，其他態樣和實施方式係可能的。本發明之其他特徵和優點將從以下詳細說明和從申請專利範圍中顯而易見。 A number of aspects and implementations have been described above, and these aspects and implementations are illustrative only and not limiting. After reading this specification, those skilled in the art will appreciate that other aspects and implementations are possible without departing from the scope of the invention. Other features and advantages of the present invention will be apparent from the following detailed description and from the claims.

根據上下文，如本文所用的「二胺(diamine)」旨在意指：(i)未反應的形式(即，二胺單體)；(ii)部分反應的形式(即，衍生自或以其他方式可歸於二胺單體的低聚物或其他聚合物先質(precursor)的一個或多個部分)或(iii)完全反應的形式(衍生自或以其他方式可歸於二胺單體的聚合物的一個或多個部分)。根據在本發明之實踐中選擇的具體實施方式，二胺可以用一個或多個部分體(moieties)予以官能化。 Depending on the context, "diamine" as used herein is intended to mean: (i) the unreacted form (i.e., the diamine monomer); (ii) the partially reacted form (i.e., derived from or otherwise oligomers or other polymer precursors attributable to diamine monomers (one or more moieties) or (iii) fully reacted forms (polymers derived from or otherwise attributable to diamine monomers) one or more parts of ). Depending on the embodiment chosen in the practice of the invention, the diamine may be functionalized with one or more moieties.

實際上，術語「二胺」不旨在限制(或字面上解釋)為二胺組分中的胺部分體(amine moieties)的數目。例如，以上(ii)和(iii)包括可以具有兩個、一個或零個胺部分體的聚合物材料。可替代地，二胺可以用附加的胺部分體(除了與二酐反應以延長聚合物鏈的單體末端處的胺部分體之外)官能化。此類附加的胺部分體可以用於交聯聚合物或用於向聚合物提供其他官能基。 Indeed, the term "diamine" is not intended to be limited (or interpreted literally) as the number of amine moieties in the diamine component. For example, (ii) and (iii) above include polymeric materials which may have two, one or zero amine moieties. Alternatively, the diamine may be functionalized with additional amine moieties (in addition to the amine moiety at the end of the monomer that reacts with the dianhydride to extend the polymer chain). Such additional amine moieties can be used to crosslink the polymer or to provide other functional groups to the polymer.

類似地，如本文所用的術語「二酐(dianhydride)」旨在意指與二胺反應(與其協作)並且組合能夠反應以形成中間體(其然後可以被固化成聚合物)的組分。根據上下文，如本文所用的「酸酐(anhydride)」可以不僅意指酸酐部分本身，而且意指酸酐部分體(anhydride moiety)的先質，如：(i)一對羧酸基團(其可以藉由脫水或相似類型的反應轉化為酸酐)；或(ii)能夠轉化成酸酐官能基的醯基鹵(例如，氯化物)酯官能基(或目前已知或將來開發的任何其他官能基)。 Similarly, the term "dianhydride" as used herein is intended to mean a component that reacts with (cooperates with) a diamine and combines with it to form an intermediate that can then be cured into a polymer. Depending on the context, "anhydride" as used herein may mean not only the anhydride moiety itself, but also precursors to the anhydride moiety, such as: (i) a pair of carboxylic acid groups (which can be to an anhydride by dehydration or a similar type of reaction); or (ii) an acyl halide (eg, chloride) ester function capable of being converted to an anhydride function (or any other function currently known or developed in the future).

根據上下文，「二酐」可以意指：(i)未反應的形式(即，二酐單體，不論酸酐官能基係處於真正的酸酐形式還是先質酸酐形式，如前面上述段落中所討論的)；(ii)部分反應的形式(即，反應自二酐單體或以其他方式可歸於二酐單體的低聚物或其他部分反應的先質聚合物組成物的一個或多個部分)或(iii)完全反應的形式(衍生自或以其他方式可歸於二酐單體的聚合物的一個或多個部分)。 Depending on the context, "dianhydride" may mean: (i) the unreacted form (i.e., the dianhydride monomer, whether the anhydride functional group is in the true anhydride or precursor anhydride form, as discussed in the preceding paragraph ); (ii) a partially reacted form (i.e., one or more portions of an oligomer or other partially reacted precursor polymer composition reacted from or otherwise attributable to dianhydride monomers) or (iii) fully reacted form (one or more parts of the polymer derived from or otherwise attributable to the dianhydride monomer).

根據在本發明之實踐中選擇的具體實施方式，二酐可以用一個或多個部分體予以官能化。實際上，術語「二酐」不旨在限制(或字面上解釋)為二酐組分中的酸酐部分體的數目。例如，(i)、(ii)和(iii)(在以上段落中)包括根據酸酐係呈先質狀態還是反應狀態可以具有兩個、一個或零個酸酐部分體的有機物質。可替代地，二酐組分可以用附加的酸酐類型部分體(除了與二胺反應以 提供聚合物的酸酐部分之外)官能化。此類附加的酸酐部分體可用於交聯聚合物或用於向聚合物提供其他官能基。 Depending on the embodiment chosen in the practice of the invention, the dianhydride may be functionalized with one or more moieties. Indeed, the term "dianhydride" is not intended to be limited (or interpreted literally) to the number of anhydride moieties in the dianhydride component. For example, (i), (ii) and (iii) (in the paragraph above) include organic species that can have two, one or zero anhydride moieties depending on whether the anhydride system is in the precursor or reacted state. Alternatively, the dianhydride component can be used with additional anhydride-type moieties (in addition to reacting with diamines to Provides functionalization of the anhydride moiety of the polymer. Such additional anhydride moieties can be used to crosslink the polymer or to provide other functional groups to the polymer.

可以使用許多聚合物製造製程中的任何一種來製備聚合物膜。不可能討論或描述在本發明之實踐中有用的所有可能的製造製程。應該理解的是，本發明之單體系統能夠在各種製造製程中提供上述有利的特性。本發明之組成物可以如本文所述製造並且可以使用任何常規或非常規的製造技術以熟悉該項技術者的許多(可能無數種)方式中的任何一種容易地製造。 Polymer films can be prepared using any of a number of polymer manufacturing processes. It is not possible to discuss or describe all possible manufacturing processes that are useful in the practice of the present invention. It should be appreciated that the monomeric system of the present invention can provide the above-mentioned advantageous properties in various manufacturing processes. The compositions of the present invention may be manufactured as described herein and may be readily manufactured in any of many (possibly innumerable) ways familiar to those skilled in the art using any conventional or non-conventional manufacturing technique.

儘管與本文所述之方法和材料類似或等效之方法和材料可以用於本發明之實踐或測試中，但是本文描述了合適之方法和材料。 Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, suitable methods and materials are described herein.

當量、濃度、或者其他值或參數以範圍、較佳的範圍、或一系列上限較佳的值和下限較佳的值給出時，這應當被理解為具體揭露了由任何範圍上限或較佳的值與任何範圍下限或較佳的值的任一配對所形成的所有範圍，而不論範圍是否被單獨揭露。當本文列舉數值範圍時，除非另外說明，否則該範圍旨在包括其端點，以及該範圍內的所有整數和分數。不旨在將本發明之範圍限制為限定範圍時列舉的具體值。 When amounts, concentrations, or other values or parameters are given in terms of ranges, preferred ranges, or a series of upper preferred values and lower preferred values, it should be understood that any range upper or preferred All ranges are formed by any pairing of the value for , with any lower limit or preferred value of the range, whether or not the range is individually disclosed. When a numerical range is recited herein, unless otherwise stated, that range is intended to include its endpoints, and all integers and fractions within the range. It is not intended that the scope of the invention be limited to the specific values recited when defining the range.

在描述某些聚合物時，應當理解，有時申請人藉由用來製造聚合物的單體或用來製造聚合物的單體的量來提及聚合物。儘管此種描述可能不包括用於描述最終聚合物的具體命名或可能不含以製程限定產品的術語，但對單體和量的任何此種提及應當被解釋為意指聚合物由那些單體或那個量的單體，以及其相應的聚合物和組成物製成。 In describing certain polymers, it should be understood that applicants are sometimes referring to the polymers by the monomers used to make the polymers or the amount of monomers used to make the polymers. While such descriptions may not include specific nomenclature used to describe the final polymer or may not contain process-defined product terminology, any such reference to monomers and amounts should be construed to mean that the polymer consists of those monomers Monomers or that amount of monomers, and their corresponding polymers and compositions.

除非特別說明，否則本文的材料、方法和實例僅是說明性的，而非旨在係限制性的。 The materials, methods, and examples herein are illustrative only and are not intended to be limiting unless otherwise specified.

如本文所用，術語「包含(comprises)」、「包含(comprising)」、「包括(includes)」、「包括(including)」、「具有(has)」、「具有(having)」或其任何其他變型均旨在涵蓋非排他性的包含。例如，包括要素列表之方法、製程、製品或設備不一定僅限於那些要素，而是可以包括未明確列出的或此類方法、製程、製品或設備所固有的其他要素。此外，除非有相反的明確說明，否則「或」係指包含性的或，而不是指排他性的或。例如，條件A或B藉由以下中的任一項滿足：A為真(或存在)且B為假(或不存在)，A為假(或不存在)且B為真(或存在)，以及A和B兩者都為真(或存在)。 As used herein, the terms "comprises", "comprising", "includes", "including", "has", "having" or any other Variations are intended to cover non-exclusive inclusions. For example, a method, process, article, or apparatus that includes a list of elements is not necessarily limited to only those elements, but may include other elements not expressly listed or inherent to such method, process, article, or apparatus. Furthermore, unless expressly stated to the contrary, "or" means an inclusive or, not an exclusive or. For example, condition A or B is satisfied by any of the following: A is true (or present) and B is false (or absent), A is false (or absent) and B is true (or present), and both A and B are true (or exist).

另外，使用「一個/種(a/an)」用於描述本發明之要素和組分。這樣做僅僅是為了方便並且給出本發明之一般意義。此描述應當被解讀為包括一個/種或至少一個/種，並且單數形式也包括複數形式，除非很明顯其另有所指。 In addition, the use of "a/an" is used to describe elements and components of the present invention. This is done merely for convenience and to give a general sense of the invention. This description should be read to include one or at least one and the singular also includes the plural unless it is obvious that it is meant otherwise.

有機溶劑 Organic solvents

用於合成本發明之聚合物的有用的有機溶劑較佳的是能夠溶解聚合物先質材料。這種溶劑應也具有相對低的沸點，如低於225℃，因此聚合物可以在中等(即，更方便且成本更低的)溫度下乾燥。小於210℃、205℃、200℃、195℃、190℃、或180℃的沸點係較佳的。 Useful organic solvents for the synthesis of the polymers of the present invention are preferably those capable of dissolving the polymer precursor material. This solvent should also have a relatively low boiling point, such as below 225°C, so the polymer can be dried at moderate (ie, more convenient and less costly) temperatures. A boiling point of less than 210°C, 205°C, 200°C, 195°C, 190°C, or 180°C is preferred.

有用的有機溶劑包括：N-甲基吡咯啶酮(NMP)、二甲基乙醯胺(DMAc)、甲基乙基酮(MEK)、N,N’-二甲基-甲醯胺(DMF)、二甲基亞碸(DMSO)、四甲基脲(TMU)、二醇***、二乙二醇二***、1,2-二甲氧基乙烷(單甘醇二甲醚)、二乙二醇二甲醚(二甘醇二甲醚)、1,2-雙-(2-甲氧基乙氧基)乙烷(三甘醇二甲醚)、γ-丁內酯和雙-(2-甲氧基乙基)醚、四氫呋喃(THF)、 乙酸乙酯、羥乙基乙酸酯二醇單乙酸酯、丙酮及其混合物。在一個實施方式中，較佳的溶劑包括N-甲基吡咯啶酮(NMP)和二甲基乙醯胺(DMAc)。 Useful organic solvents include: N-methylpyrrolidone (NMP), dimethylacetamide (DMAc), methyl ethyl ketone (MEK), N,N'-dimethyl-formamide (DMF ), dimethylsulfoxide (DMSO), tetramethylurea (TMU), glycol ethyl ether, diethylene glycol diethyl ether, 1,2-dimethoxyethane (monoglyme), di Ethylene glycol dimethyl ether (diglyme), 1,2-bis-(2-methoxyethoxy)ethane (triglyme), gamma-butyrolactone and bis- (2-methoxyethyl) ether, tetrahydrofuran (THF), Ethyl acetate, hydroxyethyl acetate glycol monoacetate, acetone and mixtures thereof. In one embodiment, preferred solvents include N-methylpyrrolidone (NMP) and dimethylacetamide (DMAc).

二胺 diamine

在一個實施方式中，合適的用於形成聚合物的二胺可以包括脂肪族二胺，如1,2-二胺基乙烷、1,6-二胺基己烷(HMD)、1,4-二胺基丁烷、1,5二胺基戊烷、1,7-二胺基庚烷、1,8-二胺基辛烷、1,9-二胺基壬烷、1,10-二胺基癸烷(DMD)、1,11-二胺基十一烷、1,12-二胺基十二烷(DDD)、1,16-十六亞甲基二胺、1,3-雙(3-胺基丙基)-四甲基二矽氧烷、反式-1,4-二胺基環己烷(CHDA)、異佛爾酮二胺(IPDA)、雙環[2.2.2]辛烷-1,4-二胺及其組合。適合於實踐本發明之其他脂肪族二胺包括具有六至十二個碳原子的那些或更長鏈二胺和更短鏈二胺的組合，只要維持聚合物的顯影性和柔性二者。長鏈脂肪族二胺可以增加柔性。 In one embodiment, suitable diamines for forming polymers may include aliphatic diamines such as 1,2-diaminoethane, 1,6-diaminohexane (HMD), 1,4 -Diaminobutane, 1,5-diaminopentane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10- Diaminodecane (DMD), 1,11-diaminoundecane, 1,12-diaminododecane (DDD), 1,16-hexamethylenediamine, 1,3- Bis(3-aminopropyl)-tetramethyldisiloxane, trans-1,4-diaminocyclohexane (CHDA), isophoronediamine (IPDA), bicyclo[2.2.2 ] Octane-1,4-diamine and combinations thereof. Other aliphatic diamines suitable for the practice of this invention include those having six to twelve carbon atoms or combinations of longer and shorter chain diamines, so long as both developability and flexibility of the polymer are maintained. Long chain aliphatic diamines can increase flexibility.

在一個實施方式中，合適的用於形成聚合物的二胺可以包括脂環族二胺(可以是完全或部分飽和的)，如環丁烷二胺(例如，順式-和反式-1,3-二胺基環丁烷、6-胺基-3-氮雜螺[3.3]庚烷和3,6-二胺基螺[3.3]庚烷)、二環[2.2.1]庚烷-1,4-二胺、異佛爾酮二胺和二環[2.2.2]辛烷-1,4二胺。其他脂環族二胺可包括順式-1,4環己烷二胺、反式-1,4環己烷二胺、1,4-雙(胺基甲基)環己烷、4,4'-亞甲基雙(環己胺)、4,4'-亞甲基雙(2-甲基-環己胺)、雙(胺基甲基)降莰烷。 In one embodiment, suitable diamines for forming polymers may include cycloaliphatic diamines (which may be fully or partially saturated), such as cyclobutane diamines (e.g., cis- and trans -1 ,3-diaminocyclobutane, 6-amino-3-azaspiro[3.3]heptane and 3,6-diaminospiro[3.3]heptane), bicyclo[2.2.1]heptane -1,4-diamine, isophoronediamine and bicyclo[2.2.2]octane-1,4-diamine. Other cycloaliphatic diamines may include cis -1,4 cyclohexanediamine, trans- 1,4 cyclohexanediamine, 1,4-bis(aminomethyl)cyclohexane, 4,4 '-methylenebis(cyclohexylamine), 4,4'-methylenebis(2-methyl-cyclohexylamine), bis(aminomethyl)norbornane.

在一個實施方式中，合適的用於形成聚合物的二胺可以包括氟化的芳香族二胺，如2,2'-雙(三氟甲基)聯苯胺(TFMB)、三氟甲基-2,4-二胺基苯、三氟甲基-3,5-二胺基苯、2,2'-雙-(4-胺基苯基)-六氟丙烷、4,4'-二胺基-2,2'-三氟甲基二苯醚、3,3'-二胺基-5,5'-三氟甲基二苯醚、9,9'-雙(4-胺基苯基)茀、4,4'-三氟甲 基-2,2'-二胺基聯苯、4,4'-氧基-雙-[(2-三氟甲基)苯胺](1,2,4-OBABTF)、4,4'-氧基-雙-[(3-三氟甲基)苯胺]、4,4'-硫代-雙-[(2-三氟甲基)苯胺]、4,4'-硫代雙[(3-三氟甲基)苯胺]、4,4'-亞硫醯基(sulfoxyl)-雙-[(2-三氟甲基)苯胺]、4,4'-亞硫醯基-雙-[(3-三氟甲基)苯胺]、4,4'-酮基-雙-[(2-三氟甲基)苯胺]、1,1-雙[4'-(4”-胺基-2”-三氟甲基苯氧基)苯基]環戊烷、1,1-雙[4'-(4”-胺基-2”-三氟甲基苯氧基)苯基]環己烷、2-三氟甲基-4,4'-二胺基二苯醚；1,4-(2'-三氟甲基-4',4”-二胺基二苯氧基)-苯、1,4-雙(4'-胺基苯氧基)-2-[(3',5'-二三氟甲基)苯基]苯、1,4-雙[2'-氰基-3'(“4-胺基苯氧基)苯氧基]-2-[(3',5'-二三氟-甲基)苯基]苯(6FC-二胺)、3,5-二胺基-4-甲基-2',3',5',6'-四氟-4'-三-氟甲基二苯醚、2,2-雙[4'(4”-胺基苯氧基)苯基]酞-3',5'-雙(三氟甲基)苯胺(6FADAP)和3,3',5,5'-四氟-4,4'-二胺基-二苯基甲烷(TFDAM)。 In one embodiment, suitable diamines for polymer formation may include fluorinated aromatic diamines such as 2,2'-bis(trifluoromethyl)benzidine (TFMB), trifluoromethyl- 2,4-diaminobenzene, trifluoromethyl-3,5-diaminobenzene, 2,2'-bis-(4-aminophenyl)-hexafluoropropane, 4,4'-diamine -2,2'-trifluoromethyl diphenyl ether, 3,3'-diamino-5,5'-trifluoromethyl diphenyl ether, 9,9'-bis(4-aminophenyl ) fennel, 4,4'-trifluoroform Base-2,2'-diaminobiphenyl, 4,4'-oxy-bis-[(2-trifluoromethyl)aniline](1,2,4-OBABTF), 4,4'-oxy Base-bis-[(3-trifluoromethyl)aniline], 4,4'-thio-bis-[(2-trifluoromethyl)aniline], 4,4'-thiobis[(3- Trifluoromethyl)aniline], 4,4'-sulfoxyl-bis-[(2-trifluoromethyl)aniline], 4,4'-sulfoxyl-bis-[(3 -trifluoromethyl)aniline], 4,4'-keto-bis-[(2-trifluoromethyl)aniline], 1,1-bis[4'-(4"-amino-2"- Trifluoromethylphenoxy)phenyl]cyclopentane, 1,1-bis[4'-(4"-amino-2"-trifluoromethylphenoxy)phenyl]cyclohexane, 2 -Trifluoromethyl-4,4'-diaminodiphenyl ether; 1,4-(2'-trifluoromethyl-4',4"-diaminodiphenoxy)-benzene, 1, 4-bis(4'-aminophenoxy)-2-[(3',5'-ditrifluoromethyl)phenyl]benzene, 1,4-bis[2'-cyano-3'( "4-aminophenoxy)phenoxy]-2-[(3',5'-bistrifluoro-methyl)phenyl]benzene (6FC-diamine), 3,5-diamino- 4-Methyl-2',3',5',6'-tetrafluoro-4'-tri-fluoromethyl diphenyl ether, 2,2-bis[4'(4"-aminophenoxy) Phenyl]phthalein-3',5'-bis(trifluoromethyl)aniline (6FADAP) and 3,3',5,5'-tetrafluoro-4,4'-diamino-diphenylmethane ( TFDAM).

用於形成聚合物的其他有用的二胺可以包括對苯二胺(PPD)、間苯二胺(MPD)、2,5-二甲基-1,4-二胺基苯、2,5-二甲基-1,4-苯二胺(DPX)、2,2-雙-(4-胺基苯基)丙烷、1,4-萘二胺、1,5-萘二胺、4,4'-二胺基聯苯、4,4"-二胺基三聯苯、4,4'-二胺基苯甲醯苯胺、4,4'-二胺基苯基苯甲酸酯、4,4'-二胺基二苯甲酮、4,4'-二胺基二苯基甲烷(MDA)、4,4'-二胺基二苯基硫醚、4,4'-二胺基二苯基碸、3,3’-二胺基二苯碸、雙-(4-(4-胺基苯氧基)苯基碸(BAPS)、4,4'-雙-(胺基苯氧基)聯苯(BAPB)、4,4'-二胺基二苯醚(ODA)、3,4'-二胺基二苯醚、4,4'-二胺基二苯甲酮、4,4’-異亞丙基二苯胺、2,2'-雙-(3-胺基苯基)丙烷、N,N-雙-(4-胺基苯基)-正丁胺、N,N-雙-(4-胺基苯基)甲胺、1,5-二胺基萘、3,3'-二甲基-4,4'-二胺基聯苯、間-胺基苯甲醯基-對-胺基苯胺、4-胺基苯基-3-胺基苯甲酸酯、N,N-雙-(4-胺基苯基)苯胺、2,4-二胺基甲苯、2,5-二胺基甲苯、2,6-二胺基甲苯、2,4-二胺 -5-氯甲苯、2,4-二胺-6-氯甲苯、2,4-雙-(β-胺基-三級丁基)甲苯、雙-(對-β-胺基-三級丁基苯基)醚、對-雙-2-(2-甲基-4-胺基戊基)苯、間苯二甲胺、以及對苯二甲胺。 Other useful diamines for forming polymers may include p-phenylenediamine (PPD), m-phenylenediamine (MPD), 2,5-dimethyl-1,4-diaminobenzene, 2,5- Dimethyl-1,4-phenylenediamine (DPX), 2,2-bis-(4-aminophenyl)propane, 1,4-naphthalenediamine, 1,5-naphthalenediamine, 4,4 '-diaminobiphenyl, 4,4"-diaminoterphenyl, 4,4'-diaminobenzanilide, 4,4'-diaminophenylbenzoate, 4,4 '-Diaminobenzophenone, 4,4'-diaminodiphenylmethane (MDA), 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl Diaminophenoxy, 3,3'-diaminophenoxy, bis-(4-(4-aminophenoxy)phenylphenoxide (BAPS), 4,4'-bis-(aminophenoxy) Biphenyl (BAPB), 4,4'-diaminodiphenyl ether (ODA), 3,4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 4,4' -Isopropylidene diphenylamine, 2,2'-bis-(3-aminophenyl)propane, N,N-bis-(4-aminophenyl)-n-butylamine, N,N-bis- (4-aminophenyl)methylamine, 1,5-diaminonaphthalene, 3,3'-dimethyl-4,4'-diaminobiphenyl, m-aminobenzoyl-p -Aminoaniline, 4-aminophenyl-3-aminobenzoate, N,N-bis-(4-aminophenyl)aniline, 2,4-diaminotoluene, 2,5- Diaminotoluene, 2,6-diaminotoluene, 2,4-diamine -5-chlorotoluene, 2,4-diamine-6-chlorotoluene, 2,4-bis-(β-amino-tertiary butyl)toluene, bis-(p-β-amino-tertiary butyl) phenyl) ether, p-bis-2-(2-methyl-4-aminopentyl)benzene, m-xylylenediamine, and p-xylylenediamine.

用於形成聚合物的其他有用的二胺可以包括1,2-雙-(4-胺基苯氧基)苯、1,3-雙-(4-胺基苯氧基)苯(RODA)、1,2-雙-(3-胺基苯氧基)苯、1,3-雙-(3-胺基苯氧基)苯、1-(4-胺基苯氧基)-3-(3-胺基苯氧基)苯、1,4-雙-(4-胺基苯氧基)苯、1,4-雙-(3-胺基苯氧基)苯、1-(4-胺基苯氧基)-4-(3-胺基苯氧基)苯、2,2-雙-(4-[4-胺基苯氧基]苯基)丙烷(BAPP)、2,2'-雙-(4-苯氧基苯胺)異亞丙基、2,4,6-三甲基-1,3-二胺基苯和2,4,6-三甲基-1,3-二胺基苯。 Other useful diamines for forming polymers may include 1,2-bis-(4-aminophenoxy)benzene, 1,3-bis-(4-aminophenoxy)benzene (RODA), 1,2-bis-(3-aminophenoxy)benzene, 1,3-bis-(3-aminophenoxy)benzene, 1-(4-aminophenoxy)-3-(3 -aminophenoxy)benzene, 1,4-bis-(4-aminophenoxy)benzene, 1,4-bis-(3-aminophenoxy)benzene, 1-(4-aminophenoxy) Phenoxy)-4-(3-aminophenoxy)benzene, 2,2-bis-(4-[4-aminophenoxy]phenyl)propane (BAPP), 2,2'-bis -(4-phenoxyaniline)isopropylidene, 2,4,6-trimethyl-1,3-diaminobenzene and 2,4,6-trimethyl-1,3-diamino benzene.

二酐 Dianhydride

在一個實施方式中，任何數量的合適的二酐可以用於形成聚合物。二酐可以以其四酸形式(或作為四酸的單、二、三或四酯)，或作為其二酯醯基鹵(氯化物)使用。然而，在一些實施方式中，二酐形式可能是較佳的，因為它通常比酸或酯更具反應性。 In one embodiment, any number of suitable dianhydrides can be used to form the polymer. Dianhydrides can be used in their tetraacid form (or as mono-, di-, tri- or tetraesters of tetraacids), or as their diester acyl halides (chlorides). However, in some embodiments, the dianhydride form may be preferred because it is generally more reactive than an acid or ester.

合適的二酐的實例包括3,3',4,4'-聯苯四甲酸二酐(BPDA)、1,2,5,6-萘四甲酸二酐、1,4,5,8-萘四甲酸二酐、2,3,6,7-萘四甲酸二酐、2-(3',4'-二羧基苯基)5,6-二羧基苯并咪唑二酐、2-(3',4'-二羧基苯基)5,6-二羧基苯并

Figure 111133737-A0202-12-0013-8
唑二酐、2-(3',4'-二羧基苯基)5,6-二羧基苯并噻唑二酐、2,2',3,3'-二苯甲酮四甲酸二酐、2,3,3',4'-二苯甲酮四甲酸二酐、3,3',4,4'-二苯甲酮四甲酸二酐(BTDA)、2,2',3,3’-聯苯四甲酸二酐、2,3,3',4'-聯苯四甲酸二酐、二環-[2,2,2]-辛烯-(7)-2,3,5,6-四甲酸-2,3,5,6-二酐、4,4'-硫代-二鄰苯二甲酸酐、雙(3,4-二羧基苯基)碸二酐、雙(3,4-二羧基苯基)亞碸二酐(DSDA)、雙(3,4-二羧基苯基
Figure 111133737-A0202-12-0013-9
二唑-1,3,4)對苯二酐、雙(3,4-二羧基苯基)2,5-
Figure 111133737-A0202-12-0013-10
二唑1,3,4-二酐、雙2,5-(3',4'-二羧基二苯醚)1,3,4-
Figure 111133737-A0202-12-0013-11
二唑二酐、 4,4'-氧基二鄰苯二甲酸酐(ODPA)、雙(3,4-二羧基苯基)硫醚二酐、雙酚A二酐(BPADA)、雙酚S二酐、雙-1,3-異苯并呋喃二酮、1,4-雙(4,4'-氧基鄰苯二甲酸酐)苯、雙(3,4-二羧基苯基)甲烷二酐、環戊二烯基四甲酸二酐、乙烯四甲酸二酐、苝3,4,9,10-四甲酸二酐、均苯四甲酸二酐(PMDA)、四氫呋喃四甲酸二酐、1,3-雙-(4,4'-氧基二鄰苯二甲酸酐)苯、2,2-雙(3,4-二羧基苯基)丙烷二酐、2,6-二氯萘-1,4,5,8-四甲酸二酐、2,7-二氯萘-1,4,5,8-四甲酸二酐、2,3,6,7-四氯萘-1,4,5,8-四甲酸二酐、菲-1,8,9,10-四甲酸二酐、吡
Figure 111133737-A0202-12-0014-5
-2,3,5,6-四甲酸二酐、苯-1,2,3,4-四甲酸二酐和噻吩-2,3,4,5-四甲酸二酐。 Examples of suitable dianhydrides include 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), 1,2,5,6-naphthalene tetracarboxylic dianhydride, 1,4,5,8-naphthalene Tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 2-(3',4'-dicarboxyphenyl)5,6-dicarboxybenzimidazole dianhydride, 2-(3',4'-dicarboxyphenyl) 5,6-dicarboxybenzo
Figure 111133737-A0202-12-0013-8
oxazole dianhydride, 2-(3',4'-dicarboxyphenyl) 5,6-dicarboxybenzothiazole dianhydride, 2,2',3,3'-benzophenone tetracarboxylic dianhydride, 2 ,3,3',4'-Benzophenone tetracarboxylic dianhydride, 3,3',4,4'-Benzophenone tetracarboxylic dianhydride (BTDA), 2,2',3,3'- Biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, bicyclo-[2,2,2]-octene-(7)-2,3,5,6- Tetracarboxylic acid-2,3,5,6-dianhydride, 4,4'-thio-diphthalic anhydride, bis(3,4-dicarboxyphenyl)diphthalic anhydride, bis(3,4- Dicarboxyphenyl) dianhydride (DSDA), bis(3,4-dicarboxyphenyl
Figure 111133737-A0202-12-0013-9
Oxadiazole-1,3,4) terephthalic anhydride, bis(3,4-dicarboxyphenyl) 2,5-
Figure 111133737-A0202-12-0013-10
Oxadiazole 1,3,4-dianhydride, bis 2,5-(3',4'-dicarboxydiphenyl ether) 1,3,4-
Figure 111133737-A0202-12-0013-11
Oxadiazole dianhydride, 4,4'-oxydiphthalic anhydride (ODPA), bis(3,4-dicarboxyphenyl) sulfide dianhydride, bisphenol A dianhydride (BPADA), bisphenol S Dianhydride, bis-1,3-isobenzofurandione, 1,4-bis(4,4'-oxyphthalic anhydride)benzene, bis(3,4-dicarboxyphenyl)methane anhydride, cyclopentadienyl tetracarboxylic dianhydride, ethylene tetracarboxylic dianhydride, perylene 3,4,9,10-tetracarboxylic dianhydride, pyromellitic dianhydride (PMDA), tetrahydrofuran tetracarboxylic dianhydride, 1, 3-bis-(4,4'-oxydiphthalic anhydride)benzene, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,6-dichloronaphthalene-1, 4,5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,3,6,7-tetrachloronaphthalene-1,4,5, 8-tetracarboxylic dianhydride, phenanthrene-1,8,9,10-tetracarboxylic dianhydride, pyridine
Figure 111133737-A0202-12-0014-5
-2,3,5,6-tetracarboxylic dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride and thiophene-2,3,4,5-tetracarboxylic dianhydride.

在一個實施方式中，合適的二酐可以包括脂環族二酐，如環丁烷-1,2,3,4-四甲酸二酐(CBDA)、1,2,4,5-環己烷四甲酸二酐、1,2,3,4-環己烷四甲酸二酐、1,2,3,4-四甲基-1,2,3,4-環丁烷四甲酸二酐、1,2,3,4-環戊烷四甲酸二酐(CPDA)、六氫-4,8-橋亞乙基-1H,3H-苯并[1,2-c：4,5-c']二呋喃-1,3,5,7-四酮(BODA)、3-(羧甲基)-1,2,4-環戊烷三甲酸1,4：2,3-二酐(TCA)、以及內消旋-丁烷-1,2,3,4-四甲酸二酐。在一個實施方式中，基於聚合物的總二酐含量，脂環族二酐可以以約70莫耳百分比或更少的量存在。 In one embodiment, suitable dianhydrides may include cycloaliphatic dianhydrides such as cyclobutane-1,2,3,4-tetracarboxylic dianhydride (CBDA), 1,2,4,5-cyclohexane Tetracarboxylic dianhydride, 1,2,3,4-cyclohexane tetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1 ,2,3,4-Cyclopentanetetracarboxylic dianhydride (CPDA), Hexahydro-4,8-Ethylene-1H,3H-Benzo[1,2-c:4,5-c'] Difuran-1,3,5,7-tetraketone (BODA), 3-(carboxymethyl)-1,2,4-cyclopentanetricarboxylic acid 1,4:2,3-dianhydride (TCA), and meso-butane -1,2,3,4-tetracarboxylic dianhydride. In one embodiment, the cycloaliphatic dianhydride may be present in an amount of about 70 mole percent or less based on the total dianhydride content of the polymer.

在一個實施方式中，合適的用於形成聚合物的二酐可以包括氟化的二酐，如4,4'-(六氟異亞丙基)二鄰苯二甲酸酐(6FDA)和9,9-雙(三氟甲基)-2,3,6,7-

Figure 111133737-A0202-12-0014-7
四甲酸二酐。 In one embodiment, suitable dianhydrides for forming the polymer may include fluorinated dianhydrides such as 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA) and 9, 9-bis(trifluoromethyl)-2,3,6,7-
Figure 111133737-A0202-12-0014-7
Tetraformic dianhydride.

在一個實施方式中，聚(醯胺-醯亞胺)可以由含醯氯的單體生產，如對苯二甲醯氯(TPCI)、間苯二甲醯氯(IPCI)、聯苯二甲醯氯(BPCI)、萘二甲醯氯、三聯苯二甲醯氯、2-氟-對苯二甲醯氯和偏苯三酸酐。 In one embodiment, poly(amide-imides) can be produced from amide chloride-containing monomers such as terephthaloyl chloride (TPCI), isophthaloyl chloride (IPCI), biphenyl dimethicone Acyl chloride (BPCI), naphthalene dicarboxyl chloride, terphenyl dicarboxyl chloride, 2-fluoro-terephthaloyl dichloride, and trimellitic anhydride.

在一個實施方式中，聚(酯-醯亞胺)可以由多元醇生產，該等多元醇可以與羧酸或酯醯鹵反應以產生酯鍵。 In one embodiment, poly(ester-imides) can be produced from polyols that can be reacted with carboxylic acids or ester halides to produce ester linkages.

二元醇組分可以是幾乎任何含有兩個可酯化羥基的醇二醇。還可以包括合適的二醇的混合物。用於本文的合適的二醇包括例如乙二醇、丙二醇、1,4-丁二醇、1,5-戊二醇、新戊二醇等。 The diol component can be almost any alcohol diol containing two esterifiable hydroxyl groups. Mixtures of suitable diols may also be included. Suitable diols for use herein include, for example, ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, and the like.

多元醇組分可以是幾乎任何含有至少3個可酯化羥基的多元醇，以便提供本發明以上所描述的合成方法的優點。可以適當地採用此類多元醇的混合物。合適的多元醇包括例如三(2-羥乙基)異氰脲酸酯、甘油、1,1,1-三羥甲基乙烷、1,1,1-三羥甲基丙烷、以及其混合物。 The polyol component can be virtually any polyol containing at least 3 esterifiable hydroxyl groups in order to provide the advantages of the above-described synthetic methods of the present invention. Mixtures of such polyols may suitably be employed. Suitable polyols include, for example, tris(2-hydroxyethyl)isocyanurate, glycerol, 1,1,1-trimethylolethane, 1,1,1-trimethylolpropane, and mixtures thereof .

在一些情況下，有用的二胺和二酐單體含有酯基團。該等單體的實例係二胺如4-胺基苯基4-胺基苯甲酸酯、4-胺基-3-甲基苯基-4-胺基苯甲酸酯和二酐如對伸苯基雙(偏苯三酸酯)二酐。 In some cases, useful diamine and dianhydride monomers contain ester groups. Examples of such monomers are diamines such as 4-aminophenyl 4-aminobenzoate, 4-amino-3-methylphenyl-4-aminobenzoate and dianhydrides such as p- Phenylbis(trimellitate) dianhydride.

在一些情況下，有用的二胺和二酐單體含有醯胺基團。該等單體的實例係二胺如4,4’-二胺基苯甲醯胺(DABAN)和二酐如N,N'-(2,2'-雙(三氟甲基)-[1,1'-聯苯基]-4,4'-二基)雙(1,3-二側氧基-1,3-二氫異苯并呋喃-5-甲醯胺)和N,N'-(9H-茀-9-亞基二-4,1-伸苯基)雙[1,3-二氫-1,3-二側氧基-5-異苯并呋喃甲醯胺]。 In some cases, useful diamine and dianhydride monomers contain amide groups. Examples of such monomers are diamines such as 4,4'-diaminobenzamide (DABAN) and dianhydrides such as N,N'-(2,2'-bis(trifluoromethyl)-[1 ,1'-biphenyl]-4,4'-diyl)bis(1,3-dipentoxy-1,3-dihydroisobenzofuran-5-carboxamide) and N,N' -(9H-Treme-9-ylidenebis-4,1-phenylene)bis[1,3-dihydro-1,3-dioxo-5-isobenzofurancarboxamide].

具有醯亞胺基團的更高階共聚物可以包括以上所描述的單體中的任一種。 Higher order copolymers having imide groups may include any of the monomers described above.

胺試劑 Amine reagent

在一個實施方式中，胺試劑，如一級胺或二級胺，可以用於將具有帶有醯亞胺基團的聚合物的聚合物層黏附至無機基材。雖然不受任何理論的 束縛，但據信胺試劑與醯亞胺反應以藉由產生醯胺鍵而產生與含醯亞胺的聚合物的共價鍵。先前的關於交聯反應的參考文獻表明，此化學反應係容易的並且可以在室溫下用一級胺或二級胺交聯劑發生(參見，例如，Y.Liu et al,J Membr Sci 189(2001),pp.231-239)。 In one embodiment, an amine reagent, such as a primary amine or a secondary amine, can be used to adhere a polymer layer having a polymer with imide groups to an inorganic substrate. Although not subject to any theory However, it is believed that the amine reagent reacts with the imide to create a covalent bond to the imide-containing polymer by creating an amide bond. Previous references to the crosslinking reaction indicate that this chemistry is facile and can occur at room temperature with primary or secondary amine crosslinkers (see, e.g., Y. Liu et al, J Membr Sci 189( 2001), pp. 231-239).

在一個實施方式中，也可以使用含醇鹽(alkoxide)的胺試劑，其可以藉由醇鹽與-SiOH基團的相互作用直接與無機表面相互作用。此外，該等胺基團可以與無機表面和存在於表面上的-SiOH基團相互作用，以幫助改進黏附性。 In one embodiment, alkoxide-containing amine reagents can also be used, which can directly interact with inorganic surfaces through the interaction of alkoxides with -SiOH groups. In addition, the amine groups can interact with inorganic surfaces and -SiOH groups present on the surface to help improve adhesion.

在一個實施方式中，含醯亞胺的聚合物可以具有一定範圍的玻璃化轉變溫度(Tg)。典型地，作為下限，層壓條件(熱量和施加壓力)將接近具有最低Tg的聚合物膜層的玻璃化轉變溫度。在一個實施方式中，聚合物膜層可以具有約300℃或更低的Tg。在一個實施方式中，層壓在具有最低Tg的聚合物膜層的Tg之下約20度至之上約50度範圍內的溫度下進行。對於非結晶(amorphous)或半結晶(semi-crystalline)的聚合物，Tg可能受若干個參數的影響。分子量的增加導致鏈端濃度的降低，導致端基區域的自由體積的減少和Tg的增加。在鏈中***剛性或非柔性基團或龐大且非柔性的側基或側接基團，由於鏈移動性降低，將增加聚合物的Tg。相反，含有柔性的單體並具有許多自由度的含醯亞胺的聚合物將降低Tg。對於該等含醯亞胺的聚合物，脂肪族醯亞胺二胺如正烷基二胺，將增加鏈移動性，增加自由體積(未被聚合物佔據的體積)並降低Tg。同樣地，交聯的增加降低鏈移動性，導致自由體積的減少和Tg的增加。此外，極性基團的存在增加了分子間力、鏈間吸引力和內聚力，導致自由體積的減少，導致Tg的增加。 In one embodiment, the imide-containing polymer can have a range of glass transition temperatures ( Tg ). Typically, as a lower limit, the lamination conditions (heat and applied pressure) will be close to the glass transition temperature of the polymer film layer with the lowest Tg . In one embodiment, the polymeric film layer may have a Tg of about 300°C or less. In one embodiment, lamination is performed at a temperature ranging from about 20 degrees below to about 50 degrees above the Tg of the polymeric film layer having the lowest Tg . For amorphous or semi-crystalline polymers, T g may be affected by several parameters. An increase in molecular weight leads to a decrease in the concentration of chain ends, resulting in a decrease in the free volume of the end group region and an increase in Tg . Insertion of rigid or inflexible groups or bulky and inflexible pendant or pendant groups in the chain will increase the Tg of the polymer due to reduced chain mobility. In contrast, imide-containing polymers containing flexible monomers with many degrees of freedom will lower the Tg . For such imide-containing polymers, aliphatic imide diamines, such as n-alkyl diamines, will increase chain mobility, increase free volume (volume not occupied by polymer) and lower Tg . Likewise, an increase in crosslinking reduces chain mobility, resulting in a decrease in free volume and an increase in Tg . In addition, the presence of polar groups increases the intermolecular forces, interchain attractive forces, and cohesion, resulting in a decrease in free volume, leading to an increase in Tg .

在一個實施方式中，可以衍生自金屬醇鹽的胺含有至少一個一級胺或二級胺；金屬原子可以是，例如，矽、鈦、鋁、鋯、鈮或鉭。在一個實施方式中，也可以使用含有多於一種金屬陽離子的醇鹽和金屬醇鹽簇的混合物。在一個實施方式中，含有一級胺的金屬醇鹽，如含胺的烷氧基矽烷，可以被預先水解以產生含胺的低聚物，基本上放大了介面處的胺的數量。 In one embodiment, the amine that may be derived from a metal alkoxide contains at least one primary or secondary amine; the metal atom may be, for example, silicon, titanium, aluminum, zirconium, niobium or tantalum. In one embodiment, mixtures of alkoxides and metal alkoxide clusters containing more than one metal cation may also be used. In one embodiment, metal alkoxides containing primary amines, such as amine-containing alkoxysilanes, can be pre-hydrolyzed to produce amine-containing oligomers, substantially amplifying the amount of amines at the interface.

在一個實施方式中，如果它含有醇鹽基團的話，則可以使用胺先質的水解和縮合產物中的至少一種。如本文所用，「水解產物」或「水解物」係指其中醇鹽取代基中的至少一個已羥被羥基替代的醇鹽。例如，在烷氧基矽烷的情況下，當附接至Si的兩個羥基縮合形成直接Si-O-Si鍵時，可以形成縮合物。以該方式，可以形成烷氧基矽烷低聚物。 In one embodiment, at least one of the hydrolysis and condensation product of an amine precursor may be used if it contains an alkoxide group. As used herein, "hydrolyzate" or "hydrolyzate" refers to an alkoxide in which at least one of the alkoxide substituents has been replaced with a hydroxyl group. For example, in the case of alkoxysilanes, a condensate can form when two hydroxyl groups attached to Si condense to form a direct Si-O-Si bond. In this way, alkoxysilane oligomers can be formed.

在一個實施方式中，可以藉由使含胺醇鹽與水接觸來形成水解物和/或縮合物。在一個實施方式中，可以藉由使含胺醇鹽與從約1至約200莫耳的水/每莫耳鍵合至氧基矽烷的矽的可水解官能基接觸來形成水解物和/或縮合物。 In one embodiment, hydrolysates and/or condensates may be formed by contacting an amine-containing alkoxide with water. In one embodiment, the hydrolyzate may be formed by contacting the amine-containing alkoxide with from about 1 to about 200 moles of water per mole of hydrolyzable functional groups bonded to the silicon of the oxysilane and/or Condensate.

在一個實施方式中，可以藉由在低級烷基醇溶劑的存在下使氧基矽烷與水接觸來形成水解物和/或縮合物。代表性的低級烷基醇溶劑包括脂肪族和脂環族的C1-C5醇，如甲醇、乙醇、正丙醇、異丙醇和環戊醇。在一個實施方式中，低級烷基醇溶劑係乙醇或甲醇。 In one embodiment, the hydrolyzate and/or condensate can be formed by contacting the oxysilane with water in the presence of a lower alkyl alcohol solvent. Representative lower alkyl alcohol solvents include aliphatic and cycloaliphatic C1-C5 alcohols such as methanol, ethanol, n-propanol, isopropanol and cyclopentanol. In one embodiment, the lower alkyl alcohol solvent is ethanol or methanol.

在一個實施方式中，可以藉由在催化一個或多個醇鹽取代基的水解並進一步可以催化所得水解物的縮合的有機酸的存在下使氧基矽烷與水接觸來形成水解物和/或縮合物。有機酸催化醇鹽取代基(如烷氧基和芳氧基)的水解，並導致在其位置上形成羥基(矽醇)基團。有機酸包含元素碳、氧和氫，視需要氮和硫，並含有至少一個不穩定的(酸性)質子。有機酸的實例包括羧酸， 如乙酸、馬來酸、草酸和甲酸，以及磺酸，如甲磺酸和甲苯磺酸。在一個實施方式中，有機酸可以具有至少約4.7的pKa。在一個實施方式中，有機酸係乙酸。 In one embodiment, the hydrolyzate may be formed by contacting the oxysilane with water in the presence of an organic acid that catalyzes the hydrolysis of one or more alkoxide substituents and may further catalyze the condensation of the resulting hydrolyzate and/or Condensate. Organic acids catalyze the hydrolysis of alkoxide substituents such as alkoxy and aryloxy groups and result in the formation of hydroxyl (silanol) groups in their place. Organic acids comprise the elements carbon, oxygen and hydrogen, optionally nitrogen and sulfur, and contain at least one labile (acidic) proton. Examples of organic acids include carboxylic acids such as acetic acid, maleic acid, oxalic acid and formic acid, and sulfonic acids such as methanesulfonic acid and toluenesulfonic acid. In one embodiment, the organic acid can have a pKa of at least about 4.7. In one embodiment, the organic acid is acetic acid.

在一些實施方式中，可以使用多胺低聚物，如聚醚胺(例如來自德克薩斯州伍德蘭茲亨斯邁公司(Huntsman Corp.,The Woodlands,TX)的Jeffamine®產品)和其他多胺單體(例如1,3,5-三(4-胺基苯氧基)苯)。該等試劑係多胺低聚物，其可以與聚合物膜層表面以及與無機基材表面上的-SiOH和其他官能基相互作用。 In some embodiments, polyamine oligomers such as polyetheramines (e.g., Jeffamine® products from Huntsman Corp., The Woodlands, TX) and others can be used. Polyamine monomers (eg 1,3,5-tris(4-aminophenoxy)benzene). These reagents are polyamine oligomers, which can interact with the surface of the polymer film layer and with -SiOH and other functional groups on the surface of the inorganic substrate.

多胺矽氧烷也可以用於促進含醯亞胺的聚合物層與無機基材之間的黏附。實例包括各種矽胺(silamine)，其係胺基官能化的矽氧烷和矽酮。實例包括聚[(1,3-(N,N-二甲基胺基)-2-丙氧基)矽氧烷]、聚[(甲基-3-胺基-1-丙氧基)矽氧烷]、聚[(1,3-(N,N-二甲基胺基)-2-丙氧基)矽氧烷]、雙(三甲基矽氧烷基)-1,3-二甲基-1,3-(N,N-(1',e'-二甲基胺基)-2'-丙氧基)矽氧烷。 Polyaminosiloxanes can also be used to promote adhesion between the imide-containing polymer layer and the inorganic substrate. Examples include various silamines, which are amine-functional siloxanes and silicones. Examples include poly[(1,3-(N,N-dimethylamino)-2-propoxy)siloxane], poly[(methyl-3-amino-1-propoxy)siloxane oxane], poly[(1,3-(N,N-dimethylamino)-2-propoxy)siloxane], bis(trimethylsiloxane)-1,3-di Methyl-1,3-(N,N-(1',e'-dimethylamino)-2'-propoxy)siloxane.

交聯先質 crosslinking precursor

在一個實施方式中，在形成聚合物膜的塗覆溶液中使用交聯先質。藉由使聚合物交聯，聚合物膜可以具有改善的機械特性、以及改善的耐化學性。在一些實施方式中，胺可以用作胺試劑和交聯先質兩者。交聯先質可以包括聚醚胺，如Jeffamine® D-230、Jeffamine® D-400、Jeffamine® D-2000、Jeffamine® D-2010、Jeffamine® D-4000、Jeffamine® ED-600、Jeffamine® ED-900、Jeffamine® D-2003、Jeffamine® EDR-148、Jeffamine® THF-100、Jeffamine® THF-170、Jeffamine® SD-2001、Jeffamine® D-205和Jeffamine® RFD-270。 In one embodiment, a crosslinking precursor is used in the coating solution that forms the polymer film. By crosslinking the polymer, the polymer film can have improved mechanical properties, as well as improved chemical resistance. In some embodiments, amines can be used as both amine reagents and crosslinking precursors. Crosslinking precursors can include polyetheramines such as Jeffamine® D-230, Jeffamine® D-400, Jeffamine® D-2000, Jeffamine® D-2010, Jeffamine® D-4000, Jeffamine® ED-600, Jeffamine® ED -900, Jeffamine® D-2003, Jeffamine® EDR-148, Jeffamine® THF-100, Jeffamine® THF-170, Jeffamine® SD-2001, Jeffamine® D-205, and Jeffamine® RFD-270.

在一個實施方式中，交聯先質可以包括芳香族一級二胺，如間苯二甲胺和對苯二甲胺。 In one embodiment, the crosslinking precursor may include aromatic primary diamines, such as m-xylylenediamine and p-xylylenediamine.

在一個實施方式中，交聯先質可以包括脂肪族一級二胺，如1,2-二胺基乙烷、1,6-二胺基己烷、1,4-二胺基丁烷、1,7-二胺基庚烷、1,8-二胺基辛烷、1,9-二胺基壬烷、1,10-二胺基癸烷(DMD)、1,11-二胺基十一烷、1,12-二胺基十二烷(DDD)、1,16-十六亞甲基二胺、1,3-雙(3-胺基丙基)-四甲基二矽氧烷、異佛爾酮二胺、雙環[2.2.2]辛烷-1,4-二胺及其組合。適用於實踐本發明之其他脂肪族二胺包括具有六至十二個碳原子的那些或者更長鏈和更短鏈二胺或脂環族二胺的組合。 In one embodiment, the crosslinking precursor may include aliphatic primary diamines such as 1,2-diaminoethane, 1,6-diaminohexane, 1,4-diaminobutane, 1 ,7-Diaminoheptane, 1,8-Diaminooctane, 1,9-Diaminononane, 1,10-Diaminodecane (DMD), 1,11-Diaminodecane Monoalkane, 1,12-diaminododecane (DDD), 1,16-hexamethylenediamine, 1,3-bis(3-aminopropyl)-tetramethyldisiloxane , isophoronediamine, bicyclo[2.2.2]octane-1,4-diamine and combinations thereof. Other aliphatic diamines suitable for use in the practice of this invention include those having six to twelve carbon atoms or combinations of longer and shorter chain diamines or cycloaliphatic diamines.

在一個實施方式中，交聯先質可以包括二級胺如哌

Figure 111133737-A0202-12-0019-12
、N,N’-二異丙基乙二胺、N,N’-二異丙基-1,3-丙二胺和N,N’-二甲基-1,3-丙二胺，以及三胺如2,4,6-三胺基嘧啶(TAP)、三聚氰胺、二伸乙基三胺、Jeffamine® T-403、Jeffamine® T-3000、Jeffamine® T-5000。此外，如以上所描述的可以用作聚合物的二胺單體的許多二胺也可以用作交聯先質。 In one embodiment, cross-linking precursors may include secondary amines such as piperine
Figure 111133737-A0202-12-0019-12
, N,N'-diisopropylethylenediamine, N,N'-diisopropyl-1,3-propylenediamine and N,N'-dimethyl-1,3-propylenediamine, and Triamines such as 2,4,6-triaminopyrimidine (TAP), melamine, diethylenetriamine, Jeffamine® T-403, Jeffamine® T-3000, Jeffamine® T-5000. In addition, many of the diamines described above that can be used as diamine monomers for polymers can also be used as crosslinking precursors.

在一個實施方式中，交聯先質可以包括一個或多個胺基團(其單獨地對於聚合物的交聯係反應性的或鈍化的)。當含有鈍化的胺基團時，交聯先質可以隨後化學轉化、熱轉化、光轉化或解離以形成至少兩種反應性胺。在一個實施方式中，經熱轉化的鈍化交聯先質也可以用作胺試劑以將聚合物膜層黏附至無機基材。在一個實施方式中，可以使用單個加熱步驟來既使聚合物交聯並將其黏附至基材。 In one embodiment, the crosslinking precursor may include one or more amine groups (which are individually reactive or inactive for crosslinking of the polymer). When containing inactivated amine groups, the crosslinking precursor can be subsequently chemically, thermally, phototransformed or dissociated to form at least two reactive amines. In one embodiment, thermally converted passivated crosslinking precursors can also be used as amine reagents to adhere polymeric film layers to inorganic substrates. In one embodiment, a single heating step can be used to both crosslink the polymer and adhere it to the substrate.

在一個實施方式中，交聯先質可以含有烷基鏈作為鈍化基團，如N-烷基或N,N-二烷基鏈，例如，甲基和三級丁基鏈。在一個實施方式中，交聯先質可以含有芳香族鈍化基團，如N-芳基和N,N-二芳基。在一個實施方式中，交聯先質可以是含有苄基鈍化基團的化合物。在一個實施方式中，交聯先質可以是含 有矽基衍生物作為鈍化基團的化合物，如三級丁基二苯基矽基。許多官能基可以充當胺對於具有醯亞胺基團的可溶性聚合物的保護基團。參見，例如，P.G.M.Wuts和T.W.Greene,Greene’s Protective Groups in Organic Synthesis[有機合成中的保護基團]，第4版，約翰威立父子出版公司(John Wiley & Sons,Inc.)(2007)(「Greene’s」)。 In one embodiment, the crosslinking precursor may contain alkyl chains as passivating groups, such as N-alkyl or N,N-dialkyl chains, eg, methyl and tertiary butyl chains. In one embodiment, the crosslinking precursor may contain aromatic inactivating groups, such as N-aryl and N,N-diaryl. In one embodiment, the crosslinking precursor may be a compound containing a benzyl inactivating group. In one embodiment, the crosslinking precursor may be a compound containing a silyl derivative as a passivating group, such as tertiary butyldiphenylsilyl. A number of functional groups can act as amine protecting groups for soluble polymers with imide groups. See, e.g., PGM Wuts and TW Greene, Greene's Protective Groups in Organic Synthesis, 4th ed., John Wiley & Sons, Inc. (2007) ("Greene's" ).

在一個實施方式中，交聯先質可以含有胺基甲酸酯作為鈍化基團。胺基甲酸酯鈍化基團可以藉由多種方法轉化以形成反應性胺。許多胺基甲酸酯可以藉由在典型地大於150℃的溫度下施加熱量而轉化以形成反應性胺。也可以使用多種化學途徑轉化胺基甲酸酯官能基以形成反應性胺。例如，鹼如三級丁醇、或酸如磷酸或三氟乙酸的引入可以用於轉化胺基甲酸酯以形成反應性胺。也可以使用光誘導的反應裂解胺基甲酸酯以形成反應性胺。在Greene’s中描述了轉化一系列胺基甲酸酯的多種方法。在一個實施方式中，交聯先質可以是含有胺基甲酸酯鈍化基團的化合物，該胺基甲酸酯鈍化基團係熱可裂解的，如三級丁氧羰基胺基甲酸酯、茀基甲氧基羰基胺基甲酸酯和苄基胺基甲酸酯，或者光可裂解的，如3,5-二甲氧基苄基胺基甲酸酯、間硝基苯基胺基甲酸酯和鄰硝基苄基胺基甲酸酯。 In one embodiment, the crosslinking precursor may contain urethane as a passivating group. Carbamate inactivating groups can be converted by a variety of methods to form reactive amines. Many urethanes can be converted to form reactive amines by applying heat at temperatures typically greater than 150°C. A variety of chemical routes can also be used to convert carbamate functional groups to form reactive amines. For example, the introduction of a base such as tert-butanol, or an acid such as phosphoric acid or trifluoroacetic acid can be used to convert carbamates to form reactive amines. Urethanes can also be cleaved using light-induced reactions to form reactive amines. Various methods for converting a range of carbamates are described in Greene's . In one embodiment, the crosslinking precursor may be a compound containing a carbamate inactivating group that is thermally cleavable, such as tertiary butoxycarbonyl carbamate , fenylmethoxycarbonylcarbamate and benzylcarbamate, or photocleavable ones such as 3,5-dimethoxybenzylcarbamate, m-nitrophenylamine carbamate and o-nitrobenzyl carbamate.

在一個實施方式中，交聯先質可以含有醯胺鈍化基團(其可以藉由引入不同的化學物質裂解以形成反應性胺)。例如，不同的化學物質可以包括鹼如氫氧化鈉或氫氧化鉀、氨、或三級胺。在其他情況下，可以使用酸如鹽酸、或酶如青黴素醯基轉移酶或α-胰凝乳蛋白酶裂解醯胺以形成反應性胺。 In one embodiment, the crosslinking precursor may contain an amide inactivating group (which can be cleaved by introducing a different chemical species to form a reactive amine). For example, different chemicals may include bases such as sodium or potassium hydroxide, ammonia, or tertiary amines. In other cases, the amide can be cleaved using an acid, such as hydrochloric acid, or an enzyme, such as penicillin transacylase or alpha-chymotrypsin, to form a reactive amine.

在一個實施方式中，含有醯胺鈍化基團的交聯先質可以光裂解如藉由用245nm光照射、或在大於65℃的溫度下熱裂解。廣泛的醯胺，如在Greene’s 中描述的那些，可以用作交聯先質。在一個實施方式中，交聯先質可以是含有醯胺鈍化基團的化合物，如乙醯胺、三氟乙醯胺、甲醯胺、磺醯胺如對甲苯磺醯胺、三氯乙醯胺、氯乙醯胺、苯乙醯胺、3-苯基丙醯胺、3-吡啶基甲醯胺、N-苯甲醯基***醯和苯甲醯胺。 In one embodiment, crosslinking precursors containing amide inactivating groups can be photocleaved, such as by irradiation with 245 nm light, or thermally cleaved at a temperature greater than 65°C. A wide range of amides, such as those described in Greene's , can be used as crosslinking precursors. In one embodiment, the cross-linking precursor can be a compound containing an amide inactivating group, such as acetamide, trifluoroacetamide, formamide, sulfonamides such as p-toluenesulfonamide, trichloroacetamide amine, chloroacetamide, phenylacetamide, 3-phenylpropanamide, 3-pyridylformamide, N-benzoylamphetamide, and benzamide.

在一個實施方式中，交聯先質可以是由酸如乙酸、丁酸、新戊酸、鹽酸或硫酸製成的銨鹽。可以用於鈍化交聯先質中的胺的銨鹽可以藉由添加有機和/或無機布朗斯台德酸(Brønsted acid)來形成。酸和含有胺的交聯先質的直接反應將形成銨鹽。可以藉由施加熱量使銨鹽解離以允許交聯。動力學抑制也由酸-銨平衡常數控制。如果溶液中沒有足夠的酸，如由酸-銨平衡常數所確定的，則銨鹽可以解離以在交聯先質中形成反應性胺。在一個實施方式中，銨鹽可以由胺與乙酸或三氟乙酸的反應製造，並且然後用加熱解離。 In one embodiment, the crosslinking precursor may be an ammonium salt made from an acid such as acetic acid, butyric acid, pivalic acid, hydrochloric acid, or sulfuric acid. Ammonium salts that can be used to passivate amines in crosslinking precursors can be formed by adding organic and/or inorganic Brønsted acids. The direct reaction of the acid and the amine-containing crosslinking precursor will form the ammonium salt. Ammonium salts can be dissociated by application of heat to allow crosslinking. Kinetic inhibition is also governed by the acid-ammonium equilibrium constant. If there is not enough acid in solution, as determined by the acid-ammonium equilibrium constant, the ammonium salt can dissociate to form a reactive amine in the crosslinking precursor. In one embodiment, ammonium salts can be produced from the reaction of amines with acetic acid or trifluoroacetic acid, and then dissociated with heat.

在一個實施方式中，交聯先質選自單一多官能先質、多種單官能先質的組合、或其混合物。 In one embodiment, the crosslinking precursor is selected from a single multifunctional precursor, a combination of multiple monofunctional precursors, or a mixture thereof.

聚合物膜 polymer film

在一個實施方式中，含有具有醯亞胺基團的聚合物的聚合物膜可以藉由將二胺和二酐(單體或其他聚醯亞胺先質形式)與溶劑一起組合以形成聚醯胺酸(polyamic acid)(也稱為聚醯胺酸(polyamide acid))溶液來生產。二酐和二胺可以約0.90至1.10的莫耳比組合。由其形成的聚醯胺酸的分子量可以藉由調節二酐和二胺的莫耳比來調節。 In one embodiment, polymer films containing polymers with imide groups can be formed by combining diamines and dianhydrides (monomers or other polyimide precursor forms) with solvents to form polyamide groups. Amino acid (polyamic acid) (also known as polyamide acid (polyamide acid)) solution to produce. The dianhydride and diamine may be combined in a molar ratio of about 0.90 to 1.10. The molecular weight of polyamic acid formed therefrom can be adjusted by adjusting the molar ratio of dianhydride and diamine.

在一個實施方式中，聚醯胺酸流延溶液源自聚醯胺酸溶液。聚醯胺酸澆鑄溶液，和/或聚醯胺酸溶液，可以視需要與轉化化學品組合，該等化學品如：(i)一種或多種脫水劑，如脂肪族酸酐(乙酸酐等)和/或芳香族酸酐；以 及(ii)一種或多種催化劑，如脂肪族三級胺(三乙胺等)、芳香族三級胺(二甲基苯胺等)和雜環三級胺(吡啶、甲基吡啶、異喹啉等)。酸酐脫水材料通常以與聚醯胺酸中醯胺酸基團的量相比莫耳過量使用。所使用的乙酸酐的量典型地是每當量(重複單元)聚醯胺酸約2.0-4.0莫耳。通常，使用相當量的三級胺催化劑。然後將如上所述分散或懸浮在溶劑中的奈米顆粒添加到聚醯胺酸溶液中。 In one embodiment, the polyamic acid casting solution is derived from a polyamic acid solution. The polyamic acid casting solution, and/or the polyamic acid solution, can optionally be combined with conversion chemicals such as: (i) one or more dehydrating agents, such as aliphatic anhydrides (acetic anhydride, etc.) and /or aromatic anhydrides; with and (ii) one or more catalysts, such as aliphatic tertiary amines (triethylamine, etc.), aromatic tertiary amines (dimethylaniline, etc.) and heterocyclic tertiary amines (pyridine, picoline, isoquinoline wait). The anhydride dehydrating material is generally used in molar excess compared to the amount of amide acid groups in the polyamide acid. The amount of acetic anhydride used is typically about 2.0-4.0 moles per equivalent (repeating unit) of polyamide acid. Typically, a considerable amount of tertiary amine catalyst is used. The nanoparticles dispersed or suspended in a solvent as described above are then added to the polyamic acid solution.

在一個實施方式中，轉化化學品可以是醯亞胺化催化劑(有時稱為「醯亞胺化促進劑」)，其可以幫助降低醯亞胺化溫度並縮短醯亞胺化時間。典型的醯亞胺化催化劑的範圍可以是鹼，如咪唑、1-甲基咪唑、2-甲基咪唑、1,2-二甲基咪唑、2-苯基咪唑、苯并咪唑、異喹啉，取代的吡啶，如甲基吡啶、二甲基吡啶，和三烷基胺以及羥基酸如羥基苯甲酸的異構物。該等催化劑的比例及其在聚醯胺酸層中的濃度將影響醯亞胺化動力學和膜特性。 In one embodiment, the conversion chemical can be an imidization catalyst (sometimes referred to as an "imidization accelerator"), which can help reduce the imidization temperature and shorten the imidization time. Typical imidization catalysts can range from bases such as imidazole, 1-methylimidazole, 2-methylimidazole, 1,2-dimethylimidazole, 2-phenylimidazole, benzimidazole, isoquinoline , substituted pyridines such as picoline, lutidine, and trialkylamines and isomers of hydroxyacids such as hydroxybenzoic acid. The ratio of these catalysts and their concentration in the polyamic acid layer will affect the imidization kinetics and membrane properties.

在一個實施方式中，將聚醯胺酸溶液和/或聚醯胺酸澆鑄溶液以約5.0重量%或10重量%至約15重量%、20重量%、25重量%、30重量%、35重量%或40重量%的濃度溶解於有機溶劑中。 In one embodiment, the polyamic acid solution and/or the polyamic acid casting solution is added at about 5.0 wt % or 10 wt % to about 15 wt %, 20 wt %, 25 wt %, 30 wt %, 35 wt % % or 40% by weight is dissolved in an organic solvent.

然後可以將溶劑化的混合物(聚醯胺酸澆鑄溶液)澆鑄或施用到載體(如環形帶或轉鼓)上以得到膜。可替代地，可以將其澆鑄在聚合物載體如PET，其他形式的Kapton®聚醯亞胺膜(例如，Kapton® HN或Kapton ® OL膜)或其他聚合物載體上。接著，可以藉由在適當溫度下加熱(熱固化)將含溶劑的膜轉化成自支撐膜。然後可以將膜與支撐體分離，如藉由拉幅定向，用持續加熱(乾燥和固化)來提供聚合物膜。 The solvated mixture (polyamic acid casting solution) can then be cast or applied onto a support such as an endless belt or drum to obtain a membrane. Alternatively, it can be cast on a polymeric support such as PET, other forms of Kapton® polyimide film (eg, Kapton® HN or Kapton® OL film), or other polymeric supports. Next, the solvent-containing film can be converted into a free-standing film by heating at an appropriate temperature (thermal curing). The film can then be separated from the support, such as by tentering, with continued heating (drying and curing) to provide a polymeric film.

用於產生含有聚醯亞胺的聚合物膜的可用方法可以見於美國專利案號5,166,308和5,298,331中，該等專利的所有教導藉由引用併入本說明書中。許多變型也是可能的，例如， Useful methods for producing polyimide-containing polymer films can be found in US Patent Nos. 5,166,308 and 5,298,331, the entire teachings of which are incorporated herein by reference. Many variants are also possible, for example,

(a)一種方法，其中，將二胺組分和二酐組分預先混合在一起，且然後將混合物在攪拌的同時分批添加到溶劑中。 (a) A method in which the diamine component and the dianhydride component are mixed together in advance, and then the mixture is added to the solvent in batches while being stirred.

(b)一種方法，其中，將溶劑添加到二胺和二酐組分的攪拌混合物中。(與以上(a)相反) (b) A method wherein the solvent is added to the stirred mixture of the diamine and dianhydride components. (Contrary to (a) above)

(c)一種方法，其中，將二胺單獨地溶解在溶劑中，且然後以允許控制反應速率的比例向其中添加二酐。 (c) A method in which diamine is dissolved alone in a solvent, and then dianhydride is added thereto at a ratio allowing control of the reaction rate.

(d)一種方法，其中，將二酐組分單獨地溶解在溶劑中，且然後以允許控制反應速率的比例向其中添加胺組分。 (d) A method in which the dianhydride component is individually dissolved in a solvent, and then the amine component is added thereto in a ratio allowing control of the reaction rate.

(e)一種方法，其中，將二胺組分和二酐組分分別溶解在溶劑中，且然後將該等溶液在反應器中混合。 (e) A method in which the diamine component and the dianhydride component are respectively dissolved in a solvent, and then the solutions are mixed in a reactor.

(f)一種方法，其中，預先形成具有過量胺組分的聚醯胺酸和具有過量二酐組分的另一聚醯胺酸，且然後使其在反應器中彼此反應，特別是以產生非無規或嵌段共聚物的這樣的方式彼此反應。 (f) A method wherein a polyamic acid having an excess of an amine component and another polyamic acid having an excess of a dianhydride component are preformed and then reacted with each other in a reactor, in particular to produce Such modes of non-random or block copolymers react with each other.

(g)一種方法，其中，首先使特定部分的胺組分和二酐組分反應，且然後使殘餘的二胺組分反應，或反之亦然。 (g) A method in which a specific part of the amine component and the dianhydride component are reacted first, and then the remaining diamine component is reacted, or vice versa.

(h)一種方法，其中，將轉化化學品(催化劑)與聚醯胺酸混合以形成聚醯胺酸流延溶液並且然後流延以形成凝膠膜。 (h) A method wherein a conversion chemical (catalyst) is mixed with polyamic acid to form a polyamic acid casting solution and then cast to form a gel film.

(i)一種方法，其中，將該等組分以部分或整體按任何順序添加到部分或全部溶劑中，此外其中部分或全部任何組分可以作為部分或全部溶劑中的溶液添加。 (i) A method wherein the components are added in part or in whole to some or all of the solvent in any order, further wherein some or all of any component may be added as a solution in some or all of the solvent.

(j)首先使二酐組分之一與二胺組分之一反應，從而得到第一聚醯胺酸之方法。然後使另一種二酐組分與另一種胺組分反應以得到第二聚醯胺酸。然後在膜形成前將醯胺酸以許多方式中的任一種組合。 (j) A method of firstly reacting one of the dianhydride components with one of the diamine components to obtain the first polyamic acid. Another dianhydride component is then reacted with another amine component to obtain a second polyamic acid. Amino acids are then combined in any of a number of ways prior to membrane formation.

在一個實施方式中，可以加熱聚醯胺酸溶液，視需要在醯亞胺化催化劑的存在下，以部分或完全醯亞胺化聚醯胺酸，將其轉化為具有醯亞胺基團的聚合物。溫度、時間、以及醯亞胺化催化劑的濃度和選擇可能影響聚醯胺酸溶液的醯亞胺化程度。較佳的是，溶液應被基本上醯亞胺化。在一個實施方式中，對於基本上聚合的溶液，如藉由紅外光譜法確定的，大於85%、大於90%、或大於95%的醯胺酸基團轉化為具有醯亞胺基團的聚合物。 In one embodiment, a solution of polyamic acid may be heated, optionally in the presence of an imidization catalyst, to partially or completely imidize the polyamic acid, converting it to a polyamide having an imide group. polymer. Temperature, time, and the concentration and choice of imidization catalyst may affect the degree of imidization of the polyamic acid solution. Preferably, the solution should be substantially imidized. In one embodiment, for a substantially polymerized solution, greater than 85%, greater than 90%, or greater than 95% of the amide acid groups are converted to polymeric compounds having amide groups, as determined by infrared spectroscopy. things.

在一個實施方式中，可以將溶劑化的混合物(基本上醯亞胺化的溶液)流延以形成聚合物膜。在另一個實施方式中，可以用抗溶劑如水或醇(例如，甲醇、乙醇、異丙醇)使溶劑化的混合物(第一基本上醯亞胺化的溶液)沈澱，並且可以分離固體聚合物樹脂。例如，可以藉由上清液的過濾、傾析、離心和傾析，氣相中的蒸餾或溶劑去除，或藉由其他已知的用於從漿料中分離固體沈澱物之方法來實現分離。在一個實施方式中，可以洗滌沈澱物以去除催化劑。洗滌後，沈澱物可以是基本上乾燥的，但是不必完全乾燥。可以將聚合物沈澱物重新溶解在第二溶劑中，如甲基異丁酮(MIBK)、甲基乙基酮(MEK)、乙酸乙酯、乙酸甲酯、甲酸乙酯、甲酸甲酯、四氫呋喃、丙酮、DMAc、NMP及其混合 物，以形成第二基本上醯亞胺化的溶液(流延溶液)，可以將其流延以形成聚合物膜。 In one embodiment, the solvated mixture (substantially imidized solution) can be cast to form a polymer film. In another embodiment, the solvated mixture (first substantially imidized solution) can be precipitated with an antisolvent such as water or an alcohol (e.g., methanol, ethanol, isopropanol) and the solid polymer can be isolated resin. Separation can be achieved, for example, by filtration, decantation, centrifugation, and decantation of the supernatant, distillation or solvent removal in the gas phase, or by other known methods for separating solid precipitates from slurries . In one embodiment, the precipitate can be washed to remove the catalyst. After washing, the precipitate can be substantially dry, but need not be completely dry. The polymer precipitate can be redissolved in a second solvent such as methyl isobutyl ketone (MIBK), methyl ethyl ketone (MEK), ethyl acetate, methyl acetate, ethyl formate, methyl formate, tetrahydrofuran , acetone, DMAc, NMP and their mixture material to form a second substantially imidized solution (casting solution) that can be cast to form a polymer film.

在一個實施方式中，基本上聚合的溶液使用具有對溶解度重要的結構特徵的單體(二胺或二酐)形成，該結構特徵包括柔性連接，例如但不限於，脂肪族間隔物、醚、硫醚、取代的胺、醯胺、酯、和酮，弱分子間相互作用，龐大取代，不共面，非線性和不對稱。結合該等特徵中的一些的二胺的實例係脂肪族二胺，如HMD、CHDA和IPDA，以及芳香族二胺，如MTB TFMB、MPD、RODA、BAPP、和3,4-ODA。結合該等特徵中的一些的二酐的實例係6FDA、BPADA、ODPA、DSDA和BODA。 In one embodiment, substantially polymeric solutions are formed using monomers (diamines or dianhydrides) with structural features important to solubility, including flexible linkages such as, but not limited to, aliphatic spacers, ethers, Thioethers, substituted amines, amides, esters, and ketones, weak intermolecular interactions, bulky substitution, non-coplanar, nonlinear and asymmetric. Examples of diamines that combine some of these characteristics are aliphatic diamines, such as HMD, CHDA, and IPDA, and aromatic diamines, such as MTB TFMB, MPD, RODA, BAPP, and 3,4-ODA. Examples of dianhydrides that combine some of these characteristics are 6FDA, BPADA, ODPA, DSDA and BODA.

在一個實施方式中，可以將溶劑化的混合物(基本上醯亞胺化的溶液)與交聯先質和著色劑如顏料或染料混合，並且然後流延以形成聚合物膜。在一個實施方式中，著色劑可以是低電導率炭黑。在另一個實施方式中，可以用反溶劑如水或醇(例如，甲醇、乙醇、異丙醇)使溶劑化的混合物(第一基本上醯亞胺化的溶液)沈澱。在一個實施方式中，可以洗滌沈澱物以去除催化劑。洗滌後，沈澱物可以是基本上乾燥的，但是不必完全乾燥。可以將聚合物沈澱物重新溶解在第二溶劑中，如甲基異丁酮(MIBK)、甲基乙基酮(MEK)、四氫呋喃(THF)、環戊酮、乙酸乙酯、丙酮、DMAc、NMP及其混合物，以形成第二基本上醯亞胺化的溶液(流延溶液)。可以向第二基本上醯亞胺化的溶液添加交聯先質和著色劑，可以然後將其流延以形成聚合物膜。在一個實施方式中，聚合物膜含有約80至約99wt%的交聯的聚合物。在一些實施方式中，聚合物膜含有在以下中的任兩者之間並包括這任兩者的交聯的聚合物：80wt%、85wt%、90 wt%、95wt%和99wt%。在又另一個實施方式中，聚合物膜含有約91wt%至約98wt%的交聯的聚合物。 In one embodiment, the solvated mixture (essentially imidized solution) can be mixed with a crosslinking precursor and a colorant, such as a pigment or dye, and then cast to form a polymer film. In one embodiment, the colorant may be low conductivity carbon black. In another embodiment, the solvated mixture (first substantially imidized solution) can be precipitated with an anti-solvent such as water or an alcohol (eg, methanol, ethanol, isopropanol). In one embodiment, the precipitate can be washed to remove the catalyst. After washing, the precipitate can be substantially dry, but need not be completely dry. The polymer precipitate can be redissolved in a second solvent such as methyl isobutyl ketone (MIBK), methyl ethyl ketone (MEK), tetrahydrofuran (THF), cyclopentanone, ethyl acetate, acetone, DMAc, NMP and mixtures thereof to form a second substantially imidized solution (casting solution). A crosslinking precursor and a colorant can be added to the second substantially imidized solution, which can then be cast to form a polymer film. In one embodiment, the polymer film contains from about 80 to about 99 wt% crosslinked polymer. In some embodiments, the polymer film contains a crosslinked polymer between and including any of the following: 80 wt%, 85 wt%, 90 wt%, 95wt% and 99wt%. In yet another embodiment, the polymer film contains from about 91 wt% to about 98 wt% crosslinked polymer.

在一個實施方式中，可以將基本上醯亞胺化的聚合物溶液流延或施用到支撐物(如環形帶或轉鼓)上，以形成膜。可替代地，可以將其澆鑄在聚合物載體如PET，其他形式的Kapton®聚醯亞胺膜(例如，Kapton® HN或Kapton ® OL膜)或其他聚合物載體上。接下來，可以藉由加熱以部分或完全除去溶劑來將含溶劑的膜轉化成膜。在本發明之一些態樣，在乾燥完成之前將膜與載體分離。最終的乾燥步驟可以在膜的尺寸支撐或穩定下進行。在其他態樣，將膜直接在載體上加熱。 In one embodiment, the substantially imidized polymer solution can be cast or applied onto a support such as an endless belt or drum to form a film. Alternatively, it can be cast on a polymeric support such as PET, other forms of Kapton® polyimide film (eg, Kapton® HN or Kapton® OL film), or other polymeric supports. Next, the solvent-containing film can be converted to a film by heating to partially or completely remove the solvent. In some aspects of the invention, the membrane is separated from the support before drying is complete. The final drying step can be performed with dimensional support or stabilization of the membrane. In other aspects, the membrane is heated directly on the support.

在一個實施方式中，聚(醯胺-醯亞胺)可以藉由醯氯與二胺和酸酐的反應形成。 In one embodiment, poly(amide-imides) can be formed by the reaction of amide chlorides with diamines and anhydrides.

在一個實施方式中，聚(酯-醯亞胺)、或聚(醯胺-醯亞胺)可以使用含酯或含醯胺的二胺或二酐以與以上所描述的那些類似之方法形成。在一個實施方式中，聚(酯-醯亞胺)可以藉由含酯的二胺或二酐的直接反應形成。在一個實施方式中，聚(醯胺-醯亞胺)可以藉由含醯胺的二胺或二酐的直接反應形成。 In one embodiment, poly(ester-imides), or poly(amide-imides), can be formed using ester- or amide-containing diamines or dianhydrides in a manner similar to those described above. . In one embodiment, poly(ester-imides) can be formed by the direct reaction of ester-containing diamines or dianhydrides. In one embodiment, poly(amide-imides) can be formed by the direct reaction of amide-containing diamines or dianhydrides.

在一個實施方式中，聚(酯-醯亞胺)可以藉由二醇與具有醯亞胺基團的含羧酸的單體的酯化形成，如美國專利案號4,383,105中所描述的。 In one embodiment, poly(ester-imides) can be formed by esterification of diols with carboxylic acid-containing monomers having imide groups, as described in US Pat. No. 4,383,105.

聚合物的交聯可以藉由各種方法確定。在一個實施方式中，聚合物的凝膠分率(gel fraction)可以藉由使用平衡溶脹法、比較交聯之前和之後的乾燥膜的重量來確定。在一個實施方式中，交聯的聚合物可以具有約20%至約100%、或約40%至約100%、或約50%至約100%、或約70%至約100%、或約85%至約100%的凝膠分率。在一個實施方式中，交聯的網路可以使用流變學方法鑒 定。可使用在特定應變、頻率和溫度下的振盪時間掃描測量來確認交聯的網路的形成。最初，損耗模量(G”)值高於儲能模量(G’)值，表明聚合物溶液表現得像黏性液體。隨時間推移，交聯的聚合物網路的形成係藉由G’和G”曲線的交叉證明的。交叉，稱為「凝膠點(gel point)」，表示當彈性組分超過該黏性的。 Crosslinking of polymers can be determined by various methods. In one embodiment, the gel fraction of a polymer can be determined by comparing the weight of the dried film before and after crosslinking using the equilibrium swelling method. In one embodiment, the crosslinked polymer may have from about 20% to about 100%, or from about 40% to about 100%, or from about 50% to about 100%, or from about 70% to about 100%, or about 85% to about 100% gel fraction. In one embodiment, cross-linked networks can be identified using rheological methods. Formation of crosslinked networks can be confirmed using oscillatory time sweep measurements at specific strains, frequencies and temperatures. Initially, the loss modulus ( G" ) value is higher than the storage modulus ( G' ) value, indicating that the polymer solution behaves like a viscous liquid. Over time, the formation of a cross-linked polymer network is achieved by G ' and the intersection of the G" curves. The crossover, called the "gel point", indicates when the elastic component exceeds the viscosity.

澆鑄溶液可以進一步包含許多添加劑中的任何一種，該等添加劑如加工助劑(例如，低聚物)、抗氧化劑、光穩定劑、阻燃添加劑、抗靜電劑、熱穩定劑、紫外線吸收劑、無機填料或各種增強劑。無機填料可包括導熱填料、金屬氧化物、無機氮化物和金屬碳化物，以及導電填料像金屬。常見的無機填料係氧化鋁、二氧化矽、金剛石、黏土、滑石、海泡石、氮化硼、氮化鋁、二氧化鈦、磷酸二鈣和熱解法金屬氧化物。也可以使用低顏色有機填料，如聚二烷基茀。常見的有機填料包括聚苯胺、聚噻吩、聚吡咯、聚伸苯基伸乙烯基、聚二烷基茀、炭黑、石墨、多壁和單壁碳奈米管和碳奈米纖維。在一個實施方式中，可以使用奈米顆粒填料和奈米顆粒膠體。 The casting solution may further comprise any of a number of additives such as processing aids (e.g., oligomers), antioxidants, light stabilizers, flame retardant additives, antistatic agents, heat stabilizers, UV absorbers, Inorganic fillers or various reinforcing agents. Inorganic fillers may include thermally conductive fillers, metal oxides, inorganic nitrides and metal carbides, and conductive fillers like metals. Common inorganic fillers are alumina, silica, diamond, clay, talc, sepiolite, boron nitride, aluminum nitride, titanium dioxide, dicalcium phosphate and fumed metal oxides. Low color organic fillers such as polydialkyl terpenes can also be used. Common organic fillers include polyaniline, polythiophene, polypyrrole, polyphenylene vinylene, polydialkylene, carbon black, graphite, multi-wall and single-wall carbon nanotubes, and carbon nanofibers. In one embodiment, nanoparticle fillers and nanoparticle colloids can be used.

在一個實施方式中，導電填料係炭黑。在一個實施方式中，導電填料選自由乙炔黑、超耐磨爐黑、導電爐黑、導電槽型炭黑、碳奈米管、碳纖維、細熱裂黑(tine thermal black)及其混合物組成之群組。如以上對於低電導率炭黑所描述的，碳顆粒的表面上的氧複合物充當電絕緣層。因此，低揮發物含量通常是高導電性所希望的。然而，還需要考慮分散炭黑的難度。表面氧化增強了炭黑的解聚和分散。在一些實施方式中，當導電填料係炭黑時，炭黑具有小於或等於1%的揮發物含量。 In one embodiment, the conductive filler is carbon black. In one embodiment, the conductive filler is selected from the group consisting of acetylene black, super wear-resistant furnace black, conductive furnace black, conductive channel black, carbon nanotubes, carbon fibers, fine thermal black (tine thermal black) and mixtures thereof group. As described above for low conductivity carbon blacks, the oxygen complexes on the surface of the carbon particles act as an electrically insulating layer. Therefore, low volatile content is generally desirable for high conductivity. However, the difficulty of dispersing carbon black also needs to be considered. Surface oxidation enhances the deagglomeration and dispersion of carbon black. In some embodiments, when the conductive filler is carbon black, the carbon black has a volatile content of less than or equal to 1%.

填料在至少一個維度上可以具有小於550nm的尺寸。在其他實施方式中，填料可以具有小於500nm、小於450nm、小於400nm、小於350nm、小 於300nm、小於250nm或小於200nm的尺寸(因為填料可以在任何維度具有多種形狀並且因為填料形狀可以沿任何維度變化，因此「至少一維」旨在係沿所述維度的數值平均值)。填料的平均縱橫比可以是1或更大。在一些實施方式中，亞微米填料選自由以下組成之群組：針狀填料(針狀)、纖維狀填料、薄片狀填料、聚合物纖維及其混合物。在一個實施方式中，亞微米填料係基本上非聚集的。亞微米填料可以是中空的、多孔的或實心的。在一個實施方式中，本揭露之亞微米填料展現出至少1、至少2、至少4、至少6、至少8、至少10、至少12、或至少15比1的縱橫比。 The filler may have a size of less than 550 nm in at least one dimension. In other embodiments, the filler can have a particle size of less than 500 nm, less than 450 nm, less than 400 nm, less than 350 nm, small A size of 300 nm, less than 250 nm, or less than 200 nm (since the filler can have multiple shapes in any dimension and because the shape of the filler can vary along any dimension, "at least one dimension" is intended to mean the numerical average along that dimension). The average aspect ratio of the filler may be 1 or greater. In some embodiments, the submicron fillers are selected from the group consisting of acicular fillers (needles), fibrous fillers, lamellar fillers, polymeric fibers, and mixtures thereof. In one embodiment, the submicron filler is substantially non-aggregated. Submicron fillers can be hollow, porous or solid. In one embodiment, the submicron fillers of the present disclosure exhibit an aspect ratio of at least 1, at least 2, at least 4, at least 6, at least 8, at least 10, at least 12, or at least 15 to 1.

在一些實施方式中，亞微米填料的尺寸係100nm或更小。在一些實施方式中，填料的形狀係球形或橢圓形，並且是奈米顆粒。在一個實施方式中，亞微米填料可以包括無機氧化物，如矽、鋁和鈦的氧化物，中空(多孔)氧化矽、氧化銻、氧化鋯、氧化銦錫、氧化銻錫、混合的鈦/錫/鋯的氧化物，以及一種或多種選自矽、鈦、鋁、銻、鋯、銦、錫、鋅、鈮和鉭的陽離子的二元、三元、四元及更高階複合氧化物。在一個實施方式中，可以使用奈米顆粒複合物(例如，單個或多個核/殼結構)，其中一種氧化物將另一種氧化物包封在一個顆粒中。 In some embodiments, the size of the submicron filler is 100 nm or less. In some embodiments, the filler is spherical or elliptical in shape and is nanoparticles. In one embodiment, submicron fillers may include inorganic oxides such as oxides of silicon, aluminum and titanium, hollow (porous) silicon oxide, antimony oxide, zirconium oxide, indium tin oxide, antimony tin oxide, mixed titanium/ Tin/zirconium oxides, and binary, ternary, quaternary and higher-order composite oxides of one or more cations selected from silicon, titanium, aluminum, antimony, zirconium, indium, tin, zinc, niobium and tantalum. In one embodiment, nanoparticle composites (eg, single or multiple core/shell structures) can be used where one oxide encapsulates another oxide within a particle.

在一個實施方式中，亞微米填料可以包括其他陶瓷化合物，如氮化硼，氮化鋁，含有硼、鋁和氮的三元或更高元化合物，氮化鎵，氮化矽，氮化鋁，硒化鋅，硫化鋅，碲化鋅，碳化矽及其組合，或含有多個陽離子和多個陰離子的更高階化合物。 In one embodiment, submicron fillers may include other ceramic compounds such as boron nitride, aluminum nitride, ternary or higher compounds containing boron, aluminum and nitrogen, gallium nitride, silicon nitride, aluminum nitride , zinc selenide, zinc sulfide, zinc telluride, silicon carbide and combinations thereof, or higher order compounds containing multiple cations and multiple anions.

在一個實施方式中，固體氧化矽奈米顆粒可以由氧化矽的溶膠(例如，固體氧化矽奈米顆粒在液體介質中的膠態分散體)，尤其是非結晶、半結晶和/或結晶二氧化矽的溶膠產生。此類溶膠可以藉由多種技術和以多種形式 製備，包括水溶膠(即，其中水充當液體介質)、有機溶膠(即，其中有機液體充當液體介質)和混合溶膠(即，其中液體介質包含水和有機液體二者)。參見，例如，在美國專利案號2,801,185、4,522,958和5,648,407中揭露的技術和形式的描述。在一個實施方式中，將奈米顆粒懸浮在極性非質子溶劑例如DMAc或與聚醯胺酸或聚(醯胺醯胺酸)相容的其他溶劑中。在另一個實施方式中，固體奈米二氧化矽顆粒可以以分散在極性非質子溶劑中的膠態分散體或溶膠的形式商業上獲得，例如像DMAC-ST(德克薩斯州休士頓的日產化學美國公司(Nissan Chemical America Corporation,Houston TX))，含有小於0.5%的水與20-21wt% SiO2的在二甲基乙醯胺中的固體二氧化矽膠體，其中中值奈米二氧化矽粒徑d50為約16nm。 In one embodiment, the solid silica nanoparticles can be formed from a sol of silica (e.g., a colloidal dispersion of solid silica nanoparticles in a liquid medium), especially amorphous, semicrystalline and/or crystalline Silica sols are produced. Such sols can be prepared by a variety of techniques and in a variety of forms, including hydrosols (i.e., in which water serves as the liquid medium), organosols (i.e., in which an organic liquid serves as the liquid medium), and mixed sols (i.e., in which the liquid medium contains water and organic liquids). See, eg, descriptions of techniques and formats disclosed in US Pat. Nos. 2,801,185, 4,522,958, and 5,648,407. In one embodiment, the nanoparticles are suspended in a polar aprotic solvent such as DMAc or other solvent compatible with polyamide acid or poly(amidoamide acid). In another embodiment, solid silica nanoparticles are commercially available in the form of colloidal dispersions or sols dispersed in polar aprotic solvents, such as DMAC-ST (Houston, Texas Nissan Chemical America Corporation, Houston TX), solid silica colloids in dimethylacetamide containing less than 0.5% water and 20-21 wt% SiO 2 , wherein the median nanometer The silica particle size d 50 is about 16 nm.

在一個實施方式中，亞微米填料可以是多孔的並且可以具有任何形狀的孔。一個實例係其中孔包括在氧化物如氧化矽的殼內形成的更低密度和低折射率的空隙(例如，含有空氣的空隙)，即中空氧化矽奈米顆粒。亞微米填料殼的厚度影響亞微米填料的強度。當使中空氧化矽顆粒具有降低的折射率和增加的孔隙率時，殼的厚度減小，導致亞微米填料的強度(即，抗斷裂性)降低。生產此類中空氧化矽奈米顆粒之方法係已知的，例如，如日本專利案號4406921 B2和4031624 B2中所述。中空氧化矽奈米顆粒可以從日本的日揮催化劑和化學品公司(JGC Catalysts and Chemicals,LTD,Japan)獲得。 In one embodiment, the submicron filler can be porous and can have pores of any shape. One example is hollow silicon oxide nanoparticles in which the pores include lower density and low index voids (eg, air-containing voids) formed within a shell of an oxide such as silicon oxide. The thickness of the submicron filler shell affects the strength of the submicron filler. When the hollow silica particles are made to have a reduced refractive index and increased porosity, the thickness of the shell is reduced, resulting in reduced strength (ie, fracture resistance) of the submicron filler. Methods for producing such hollow silica nanoparticles are known, for example, as described in Japanese Patent Publication Nos. 4406921 B2 and 4031624 B2. Hollow silica nanoparticles can be obtained from JGC Catalysts and Chemicals, LTD, Japan.

在一個實施方式中，亞微米填料可以塗覆有偶合劑。例如，奈米顆粒可以塗覆有衍生自相應的烷氧基矽烷的胺基矽烷、苯基矽烷、丙烯酸或甲基丙烯酸偶合劑。可以藉由亞微米填料與六甲基二矽氮烷的反應將三甲基矽基表面封端劑引入奈米顆粒表面。在一個實施方式中，亞微米填料可以塗覆有分散劑。在一個實施方式中，亞微米填料可以塗覆有偶合劑和分散劑的組合。可替代 地，可以將偶合劑、分散劑或其組合直接摻入聚合物膜中並且不一定塗覆到亞微米填料上。 In one embodiment, submicron fillers can be coated with coupling agents. For example, nanoparticles can be coated with aminosilanes, phenylsilanes, acrylic or methacrylic coupling agents derived from the corresponding alkoxysilanes. Trimethylsilyl-based surface capping agents can be introduced to the surface of nanoparticles by reacting submicron fillers with hexamethyldisilazane. In one embodiment, the submicron filler can be coated with a dispersant. In one embodiment, submicron fillers can be coated with a combination of coupling and dispersing agents. replaceable Alternatively, the coupling agent, dispersant, or combination thereof can be incorporated directly into the polymer film and not necessarily coated onto the submicron filler.

根據膜的預期目的或最終應用規格，可以調節聚合物膜的厚度。在一個實施方式中，聚醯亞胺膜具有約10至約80μm、或約10至約25μm、或約15至約25μm的總厚度。 Depending on the intended purpose of the film or end application specifications, the thickness of the polymer film can be adjusted. In one embodiment, the polyimide film has an overall thickness of about 10 to about 80 μm, or about 10 to about 25 μm, or about 15 to about 25 μm.

在一個實施方式中，當用雙光束分光光度計，使用D65照明和10度觀察器，在360至780nm波長範圍內以全透射模式測量時，對於約25μm的膜厚度，聚合物膜具有小於約1.25、或小於約1.0或小於約0.8的b*。在一個實施方式中，當使用ASTM E313描述的程序測量時，對於約25μm的膜厚度，聚合物膜具有小於約2.25、或小於約2.0或小於約1.75的黃度指數(YI)。 In one embodiment, the polymer film has a film thickness of less than about 25 μm when measured in full transmission mode with a dual-beam spectrophotometer using D65 illumination and a 10 degree observer in the wavelength range of 360 to 780 nm. A b* of 1.25, or less than about 1.0, or less than about 0.8. In one embodiment, the polymeric film has a yellowness index (YI) of less than about 2.25, or less than about 2.0, or less than about 1.75 for a film thickness of about 25 μm when measured using the procedure described in ASTM E313.

無機基材 Inorganic substrate

在一個實施方式中，製品可以包括與無機基材組合使用的聚合物膜層。在一個實施方式中，無機基材可以是含有矽和氧的無機材料。無機基材可以是結晶的無機材料或係非結晶的。基材可以是膜或層，或其他形狀(例如，楔形、棱柱)，包括任何角度或彎曲的幾何形狀。基材可以是棒、圓柱體或板。高壓釜層壓製程可以尤其適用於將非平面材料黏合到非平面基材上。在一個實施方式中，無機基材可以包括陶瓷、玻璃或玻璃-陶瓷材料、或其混合物。 In one embodiment, an article may include a polymeric film layer used in combination with an inorganic substrate. In one embodiment, the inorganic substrate may be an inorganic material containing silicon and oxygen. The inorganic substrate can be a crystalline inorganic material or be amorphous. The substrate can be a film or layer, or other shape (eg, wedge, prism), including any angular or curved geometry. The substrate can be a rod, cylinder or plate. Autoclave lamination processes may be especially useful for bonding non-planar materials to non-planar substrates. In one embodiment, the inorganic substrate may comprise ceramic, glass or glass-ceramic materials, or mixtures thereof.

在一個實施方式中，含有矽和氧的陶瓷基材可以包括氧化物、氮化物或氮氧化物、磷化物或磷氧化物、碳化物或碳氧化物。在一些情況下，基材可以包括氧化矽表面，但遠離基材的表面具有不同的主體組成。例如，Si3N4或SiC基材可以被水解或氧化，使得其在表面處含有矽和氧。也可以使用多層無機基材。氧化矽或含矽和含氧的無機物質的塗層可以用在無機基材上。塗層可以以 多種方式形成，包括物理氣相沈積、濺射、原子層沈積等。也可以藉由基於液體的塗覆製程(噴塗、狹縫模具塗覆、棒塗)，例如使用烷氧基矽烷作為塗層中的一種組分，製成含有矽和氧的塗層。無機基材上的表面不必僅具有矽和氧。可以使用混合相或相的組合，只要表面包括矽和氧。 In one embodiment, the silicon and oxygen containing ceramic substrate may comprise oxides, nitrides or oxynitrides, phosphides or phosphorus oxides, carbides or oxycarbides. In some cases, the substrate may include a silicon oxide surface, but the surface away from the substrate has a different bulk composition. For example, a Si3N4 or SiC substrate can be hydrolyzed or oxidized so that it contains silicon and oxygen at the surface. Multilayer inorganic substrates may also be used. Coatings of silicon oxide or inorganic substances containing silicon and oxygen can be applied to inorganic substrates. Coatings can be formed in a variety of ways, including physical vapor deposition, sputtering, atomic layer deposition, and others. Coatings containing silicon and oxygen can also be produced by liquid-based coating processes (spray coating, slot die coating, rod coating), for example using alkoxysilanes as a component in the coating. A surface on an inorganic substrate need not have only silicon and oxygen. Mixed phases or combinations of phases can be used as long as the surface includes silicon and oxygen.

在一個實施方式中，無機基材可以是各種形狀和幾何形狀的玻璃基材。如本文所用的術語「玻璃」意指包括至少部分由玻璃(包括玻璃和玻璃-陶瓷)製成的任何材料。「玻璃-陶瓷(Glass-ceramics)」包括藉由玻璃的受控結晶產生的材料。在一些實施方式中，玻璃-陶瓷具有約30%至約90%的結晶度。可以使用的玻璃-陶瓷系統的非限制性實例包括Li2O x AI2O3 x nSiO2(即，LAS系統)、MgO x Al2O3 x nSiO2(即，MAS系統)、以及ZnO x Al2O3 x nSiO2(即，ZAS系統)。 In one embodiment, the inorganic substrate can be a glass substrate of various shapes and geometries. The term "glass" as used herein is meant to include any material made at least in part of glass, including glass and glass-ceramics. "Glass-ceramics" includes materials produced by controlled crystallization of glass. In some embodiments, the glass-ceramic has a crystallinity of about 30% to about 90%. Non-limiting examples of glass-ceramic systems that can be used include Li2OxAI2O3xnSiO2 (i.e., the LAS system), MgOxAl2O3xnSiO2 ( i.e. , the MAS system ), and ZnOx Al 2 O 3 x nSiO 2 (ie, ZAS system).

在一個或多個實施方式中，無機基材可以包括玻璃，其可以是強化的或非強化的。合適的玻璃的實例包括鈉鈣玻璃、鹼鋁矽酸鹽玻璃、含鹼的硼矽酸鹽玻璃和鹼鋁硼矽酸鹽玻璃。在一些變體中，玻璃可以不含氧化鋰。在一個或多個替代實施方式中，基材可以包括結晶的基材，如玻璃-陶瓷基材(其可以是強化的或非強化的)，或可以包括單晶結構，如藍寶石。在一個或多個具體實施方式中，基材包括非結晶基體(例如，玻璃)和結晶包層(例如，藍寶石層、多晶氧化鋁層和/或尖晶石(MgAl2O4)層。 In one or more embodiments, the inorganic substrate can include glass, which can be strengthened or unstrengthened. Examples of suitable glasses include soda lime glass, alkali aluminosilicate glass, alkali containing borosilicate glass and alkali aluminoborosilicate glass. In some variations, the glass may be free of lithium oxide. In one or more alternative embodiments, the substrate may comprise a crystalline substrate, such as a glass-ceramic substrate (which may be strengthened or unstrengthened), or may comprise a single crystal structure, such as sapphire. In one or more specific embodiments, the substrate includes an amorphous matrix (eg, glass) and a crystalline cladding (eg, a layer of sapphire, a layer of polycrystalline alumina, and/or a layer of spinel (MgAl 2 O 4 ).

基材或層可以被強化以形成強化的基材或層。如本文所用，術語「強化基材(strengthened substrate)」或「強化層(strengthened layer)」可以是指已經被化學強化的基材和/或層，例如藉由基材和/或層的表面中的更大離子對更小離子的離子交換。本領域已知的其他強化方法，如熱回火，或利用基材和/或層 的部分之間的熱膨脹係數不匹配來產生壓縮應力和中心張力區域，也可以用於形成強化的基材和/或層。 A substrate or layer can be strengthened to form a strengthened substrate or layer. As used herein, the term "strengthened substrate" or "strengthened layer" may refer to a substrate and/or layer that has been chemically strengthened, for example by Ion exchange of larger ions for smaller ions. Other strengthening methods known in the art, such as thermal tempering, or utilizing substrates and/or layers CTE mismatches between parts to create compressive stresses and central tension regions can also be used to form reinforced substrates and/or layers.

在基材和/或層藉由離子交換方法進行化學強化時，基材和/或層的表面層中的離子被具有相同價態或氧化態的更大的離子替代，或與其交換。離子交換方法典型地藉由將基材和/或層浸入含有待與基材中的更小離子交換的更大離子的熔融鹽浴中進行。熟悉該項技術者將理解，離子交換方法的參數，包括但不限於浴組成和溫度、浸入時間、基材和/或層在一個或多個鹽浴中的浸入次數、多個鹽浴的使用、附加步驟(如退火、洗滌等)，通常由基材和/或層的組成以及強化操作所產生的基材的希望壓縮應力(CS)、壓縮應力層深度(或層深度)確定。舉例來說，含鹼金屬的玻璃基材和/或層的離子交換可以藉由浸入至少一個含有鹽的熔融浴中來實現，該鹽如但不限於更大鹼金屬離子的硝酸鹽、硫酸鹽和氯化物。熔融鹽浴的溫度典型地在約380℃至約450℃的範圍內，而浸入時間在約15分鐘至約40小時的範圍內。然而，也可以使用與上述那些不同的溫度和浸入時間。 When a substrate and/or layer is chemically strengthened by ion exchange methods, ions in the surface layers of the substrate and/or layer are replaced or exchanged with larger ions of the same valence or oxidation state. The ion exchange process is typically performed by immersing the substrate and/or layer in a molten salt bath containing larger ions to be exchanged with smaller ions in the substrate. Those skilled in the art will appreciate that the parameters of the ion exchange process, including but not limited to bath composition and temperature, immersion time, number of immersions of the substrate and/or layer in one or more salt baths, use of multiple salt baths , additional steps (such as annealing, washing, etc.), usually determined by the composition of the substrate and/or layers and the desired compressive stress (CS) of the substrate produced by the strengthening operation, the compressive stress layer depth (or layer depth). For example, ion exchange of alkali metal-containing glass substrates and/or layers can be achieved by immersion in at least one molten bath containing salts such as, but not limited to, nitrates, sulfates of larger alkali metal ions and chlorides. The temperature of the molten salt bath is typically in the range of about 380°C to about 450°C, and the immersion time is in the range of about 15 minutes to about 40 hours. However, temperatures and immersion times other than those described above may also be used.

此外，離子交換方法的非限制性實例，其中將玻璃基材和/或層浸入多個離子交換浴中，在浸入之間具有洗滌和/或退火步驟，描述於美國專利案號8,561,429中，其中玻璃基材藉由浸入不同濃度的鹽浴中進行多個、連續的離子交換處理來強化；以及美國專利8,312,739中，其中玻璃基材藉由在用流出物離子稀釋的第一浴中進行離子交換，然後浸入具有比第一浴更小的流出物離子濃度的第二浴中來強化。 Additionally, a non-limiting example of an ion exchange process, wherein glass substrates and/or layers are immersed in multiple ion exchange baths with washing and/or annealing steps between immersions, is described in U.S. Pat. No. 8,561,429, wherein Glass substrates are strengthened by immersion in salt baths of varying concentrations for multiple, sequential ion exchange treatments; and U.S. Patent No. 8,312,739, where glass substrates are ion exchanged by ion exchange in a first bath diluted with effluent ions , and then fortified by immersion in a second bath having a lower effluent ion concentration than the first bath.

在一個實施方式中，使用浸塗製程使用具有含矽的胺試劑的溶液來處理無機基材。含矽的胺試劑可以具有醇鹽基團。胺試劑包括一級胺或二級 胺，並且乾燥後，無機基材具有胺官能表面。隨後，可以用熱量和壓力將基材層壓至聚合物膜，該膜包括具有醯亞胺基團的聚合物。無機表面上的胺可以與聚合物反應以形成醯胺並為基材提供矽氧烷鍵。 In one embodiment, the inorganic substrate is treated with a solution having a silicon-containing amine reagent using a dip coating process. Silicon-containing amine reagents can have alkoxide groups. Amine reagents include primary amines or secondary amine, and after drying, the inorganic substrate has an amine-functional surface. The substrate can then be laminated to a polymer film comprising a polymer having imide groups using heat and pressure. Amines on inorganic surfaces can react with polymers to form amides and provide siloxane linkages to the substrate.

層壓(Lamination) Lamination

聚合物膜的黏附可以藉由在液壓機中施加壓力的同時加熱來完成。典型地，在層壓製程期間達到的最高溫度不低於具有最低Tg的聚合物膜層的Tg之下20℃。可以使用更高的溫度用於層壓，但在高於具有最低Tg的聚合物的Tg之上50℃的溫度下，如果在更高溫度下的停留時間為五分鐘或更長，則可能發生膜的一些變色。因此，更高溫度層壓可能需要短於5分鐘的停留時間。在液壓機中層壓可以是在空氣中或在真空下以幫助去除截留的空氣。可以將胺試劑施加至該等聚合物膜之一的表面、或施加至每個聚合物膜的一個表面。可以使用任何使聚合物膜與可溶性胺試劑接觸之方法，包括棒塗、狹縫模具塗覆、噴塗、浸塗、旋塗或其他液體塗覆方法。在一個實施方式中，一個或多個聚合物膜層的表面可以在層壓之前進行電漿處理或電暈處理，以進一步增強聚合物膜層的黏附。任何電漿或電暈處理都將在用胺試劑處理之前進行。在一個實施方式中，層壓在具有最低Tg的聚合物膜層的Tg之下約20度至之上約50度範圍內的溫度下進行。 Adhesion of the polymer film can be accomplished by applying pressure while applying heat in a hydraulic press. Typically, the highest temperature reached during the lamination process is not lower than 20°C below the Tg of the polymer film layer having the lowest Tg . Higher temperatures can be used for lamination, but at temperatures 50°C above the Tg of the polymer with the lowest Tg , if the dwell time at the higher temperature is five minutes or more, then Some discoloration of the film may occur. Therefore, higher temperature lamination may require dwell times shorter than 5 minutes. Lamination can be in air or under vacuum in a hydraulic press to help remove entrapped air. The amine reagent can be applied to the surface of one of the polymer films, or to one surface of each polymer film. Any method of contacting the polymer film with the soluble amine reagent can be used, including bar coating, slot die coating, spray coating, dip coating, spin coating, or other liquid coating methods. In one embodiment, the surface of one or more polymeric film layers may be plasma treated or corona treated prior to lamination to further enhance the adhesion of the polymeric film layers. Any plasma or corona treatment will be performed prior to treatment with amine reagents. In one embodiment, lamination is performed at a temperature ranging from about 20 degrees below to about 50 degrees above the Tg of the polymeric film layer having the lowest Tg .

在一個實施方式中，可以使用高壓釜層壓製程黏附聚合物膜層。高壓釜係可以用於以間歇製程生產層壓結構的高溫壓力容器。層壓部件在裝入壓力容器腔室之前進行組裝並以這樣的方式佈置，使得它們在熱和壓力下時不移動。該製程通常使用空氣或惰性氣體(如氬氣或氮氣)操作以提供壓力，以將壓力容器腔室內的材料層壓。然後藉由不同的循環，使用熱交換器加熱和冷卻內部的氣體，以在設定的時間段內維持不同的溫度和壓力分佈。在一個實施方式 中，製程循環將在約100至約400psig和約100至約400℃的範圍內，總循環時間累積最高達約30小時。循環完成並且腔室恢復至環境溫度和壓力後，移出內容物。在一個實施方式中，高壓釜層壓在具有最低Tg的聚合物膜層的Tg之下約20度至之上約50度範圍內的溫度下進行。 In one embodiment, the polymeric film layers may be attached using an autoclave lamination process. The autoclave system can be used to produce high temperature pressure vessels with laminated structures in a batch process. The laminated parts are assembled prior to loading into the pressure vessel chamber and arranged in such a way that they do not move while under heat and pressure. The process is typically operated using air or an inert gas such as argon or nitrogen to provide the pressure to laminate the materials within the pressure vessel chamber. The gas inside is then heated and cooled using heat exchangers through different cycles to maintain different temperature and pressure profiles for a set period of time. In one embodiment, the process cycle will be in the range of about 100 to about 400 psig and about 100 to about 400°C, with a cumulative total cycle time of up to about 30 hours. After the cycle is complete and the chamber returns to ambient temperature and pressure, the contents are removed. In one embodiment, autoclave lamination is performed at a temperature ranging from about 20 degrees below to about 50 degrees above the Tg of the polymeric film layer having the lowest Tg .

在一個實施方式中，可以使用卷對卷製程(roll-to-roll process)來形成本發明之層壓製品。在此種製程中，該等聚合物膜層由輥供應並首先藉由張力輥。可以用胺試劑處理待層壓以形成該等層之間的介面的一個或兩個表面。 In one embodiment, a roll-to-roll process may be used to form laminates of the present invention. In this process, the polymer film layers are supplied from rolls and first passed over tension rolls. One or both surfaces to be laminated to form the interface between the layers may be treated with an amine agent.

在一個實施方式中，可以使用夾輥(nip-roll)層壓，其中可以加熱夾輥以促進該等聚合物膜層的黏合。由夾輥施加的黏合壓力可以隨膜材料、聚合物材料和所採用的溫度而變化。適當控制速度和張力將使膜的起皺最小化。在一個實施方式中，夾輥的溫度在具有最低Tg的聚合物膜層的Tg之下約20度至之上約50度的範圍內。 In one embodiment, nip-roll lamination can be used, where the nip-roll can be heated to facilitate adhesion of the polymeric film layers. The bonding pressure applied by the nip rolls can vary with the film material, polymer material and temperature employed. Proper control of speed and tension will minimize wrinkling of the membrane. In one embodiment, the nip roll temperature ranges from about 20 degrees below the Tg of the polymer film layer having the lowest Tg to about 50 degrees above.

黏合後，使層壓物藉由一系列的冷卻輥，這確保在輥上卷起的層壓物不發黏。製程水冷卻通常足以實現該目的。系統內的張力可以使用空轉輥(idler roll)進一步維持。藉由該製程製成的層壓製品將具有足夠的強度，以允許藉由層壓機進一步處理，這可以在層壓物上增加附加的層。 After bonding, the laminate is passed through a series of chilled rolls, which ensures that the laminate rolled up on the rolls is not sticky. Process water cooling is usually sufficient for this purpose. Tension in the system can be further maintained using idler rolls. Laminates made by this process will have sufficient strength to allow further processing by a laminator, which can add additional layers to the laminate.

在一個實施方式中，可以使用胺試劑將任意數量的聚合物膜層層壓在一起，以改進該等層中的一些或所有之間的黏附。在一個實施方式中，可以使用胺試劑將聚合物膜層和一個或多個無機基材的組合層壓在一起，以改進該等層中的一些或所有之間的黏附。 In one embodiment, any number of polymeric film layers may be laminated together using an amine reagent to improve adhesion between some or all of the layers. In one embodiment, a combination of polymeric film layers and one or more inorganic substrates can be laminated together using an amine agent to improve adhesion between some or all of the layers.

在一個實施方式中，可以形成多層聚合物膜，其中首先使用共擠出或塗覆製程形成一些層，並且然後使用使用胺試劑的層壓方法添加附加的層、 或組合任意數量的多層聚合物膜。在一些實施方式中，可以使用共擠出製程來形成多層聚合物膜，其中內芯層夾在兩個外層之間。在該製程中，將成品聚醯胺酸溶液過濾並泵送至狹縫模具，在其中將流以形成三層共擠出膜的第一外層和第二外層的方式分開。在一些實施方式中，過濾聚醯亞胺的第二束流，然後以形成三層共擠出膜的中間聚醯亞胺芯層的方式將其泵送至澆鑄模具。溶液流速可以被調節來實現希望的層厚度。 In one embodiment, a multilayer polymer film can be formed where some layers are first formed using a coextrusion or coating process, and then additional layers are added using a lamination method using an amine reagent, Or combine any number of multilayer polymer films. In some embodiments, a coextrusion process can be used to form a multilayer polymeric film in which an inner core layer is sandwiched between two outer layers. In this process, the finished polyamic acid solution is filtered and pumped to a slot die where the stream is divided in such a way that a first outer layer and a second outer layer of a three-layer coextruded film are formed. In some embodiments, the second stream of polyimide is filtered and then pumped to the casting die in such a way as to form the middle polyimide core layer of the three-layer coextruded film. The solution flow rate can be adjusted to achieve the desired layer thickness.

在一些實施方式中，多層膜藉由同時擠出第一外層、芯層和第二外層來製備。在一些實施方式中，該等層通過單腔或多腔擠出模具擠出。在另一個實施方式中，多層膜使用單腔模具來產生。如果使用單腔模具，流的層流應具有足夠高的黏度以防止流的混合並提供均勻的分層。在一些實施方式中，多層膜藉由從狹縫模具澆鑄到移動的不銹鋼帶上製備。在一個實施方式中，然後使帶通過對流烘箱，以蒸發溶劑並部分地使聚合物醯亞胺化來產生「生」膜(“green”film)。生膜可以從澆鑄帶剝離並卷起。生膜然後可以藉由拉幅機烘箱以產生完全固化的聚醯亞胺膜。在一些實施方式中，在拉幅期間，可以藉由沿著邊緣約束膜(即，使用夾子或銷)來使收縮最小化。在一個實施方式中，然後可以使用胺試劑將該三層共擠出聚合物膜進一步層壓至一個或多個附加的聚合物層、無機基材、或附加的聚合物層和無機基材。 In some embodiments, a multilayer film is prepared by simultaneously extruding a first outer layer, a core layer, and a second outer layer. In some embodiments, the layers are extruded through a single or multi-cavity extrusion die. In another embodiment, the multilayer film is produced using a single cavity mold. If a single cavity mold is used, the laminar flow of the stream should have a viscosity high enough to prevent mixing of the streams and provide uniform layering. In some embodiments, multilayer films are prepared by casting from a slot die onto a moving stainless steel belt. In one embodiment, the tape is then passed through a convection oven to evaporate the solvent and partially imide the polymer to produce a "green" film. The green film can be peeled from the casting tape and rolled up. The green film can then be passed through a tenter oven to produce a fully cured polyimide film. In some embodiments, shrinkage can be minimized by constraining the film along the edges (ie, using clips or pins) during tentering. In one embodiment, the three-layer coextruded polymer film can then be further laminated to one or more additional polymer layers, an inorganic substrate, or an additional polymer layer and an inorganic substrate using an amine reagent.

金屬包層的層壓物 Metal Clad Laminates

在一個實施方式中，可以使用具有多個聚合物膜的製品來形成金屬包層的層壓物。在一個實施方式中，用於金屬包層的層壓物的導電層可以藉由以下方式產生： In one embodiment, an article having multiple polymer films can be used to form a metal-clad laminate. In one embodiment, the conductive layer for the metal clad laminate can be produced by:

i.金屬濺射(視需要，然後電鍍)； i. Metal sputtering (if desired, followed by electroplating);

ii.箔層壓；和/或 ii. foil lamination; and/or

iii.用於將薄金屬層施加至基材上的任何常規或非常規之方法。 iii. Any conventional or non-conventional method for applying a thin metal layer to a substrate.

金屬包層的層壓物可以藉由許多熟知之方法形成為單面層壓物或雙面層壓物。在一個實施方式中，層壓製程可以用於形成具有多層聚合物膜的金屬包層的層壓物。在一個實施方式中，多層聚合物膜的第一外層包括第一熱塑性聚合物並置於第一導電層與芯層之間，並且第二外層包括第二熱塑性聚合物並置於芯層的相反側上。在一個實施方式中，第二導電層放置成與在芯層相反的側上的第二外層接觸。該類型的構造的一個優點在於，多層膜的層壓溫度降低至外層的熱塑性聚合物結合至一個或多個導電層所需要的層壓溫度。在一個實施方式中，一個或多個導電層係一個或多個金屬層。 Metal-clad laminates can be formed as single-sided or double-sided laminates by a number of well-known methods. In one embodiment, a lamination process may be used to form a metal-clad laminate with a multilayer polymer film. In one embodiment, the first outer layer of the multilayer polymeric film comprises a first thermoplastic polymer and is disposed between the first conductive layer and the core layer, and the second outer layer comprises a second thermoplastic polymer and is disposed on the opposite side of the core layer . In one embodiment, the second conductive layer is placed in contact with the second outer layer on the opposite side of the core layer. One advantage of this type of construction is that the lamination temperature of the multilayer film is lowered to that required for the thermoplastic polymer of the outer layers to bond to the one or more conductive layers. In one embodiment, the one or more conductive layers are one or more metal layers.

例如，在將聚合物膜施加到金屬箔上的步驟之前，該聚合物膜可以經受預處理步驟。預處理步驟可以包括熱處理、電暈處理、在大氣壓下的電漿處理、在減壓下的電漿處理、用偶合劑像矽烷和鈦酸鹽處理、噴砂、鹼處理、酸處理和塗覆聚醯胺酸。為了改進黏附強度，通常還可以添加各種金屬化合物，如美國專利案號4,742,099；5,227,244；5,218,034；和5,543,222中所揭露的，將它們藉由引用結合在此。 For example, the polymer film may be subjected to a pretreatment step prior to the step of applying the polymer film to the metal foil. Pretreatment steps may include heat treatment, corona treatment, plasma treatment at atmospheric pressure, plasma treatment under reduced pressure, treatment with coupling agents like silanes and titanates, sandblasting, alkali treatment, acid treatment and coating poly Amino acid. To improve adhesion strength, various metal compounds can also typically be added, as disclosed in US Pat. Nos. 4,742,099; 5,227,244; 5,218,034; and 5,543,222, which are incorporated herein by reference.

另外，(出於改進黏附的目的)導電金屬表面可以用各種有機處理和無機處理進行處理。該等處理包括使用矽烷、咪唑、***、氧化物和還原性氧化物處理、氧化錫處理和經由酸或鹼試劑進行的表面清潔/粗糙化(稱為微蝕刻)。 In addition, (for the purpose of improving adhesion) conductive metal surfaces can be treated with various organic and inorganic treatments. These treatments include treatment with silanes, imidazoles, triazoles, oxides and reducing oxides, tin oxide treatment and surface cleaning/roughening by acid or alkaline agents (known as microetching).

如本文所用，術語「導電層(conductive layers)」和「導電箔(conductive foils)」意指金屬層或金屬箔(具有高等級銅的電導率的至少50%的薄 的組成物)。導電箔典型地是金屬箔。金屬箔不必作為純的形式的元素使用；其也可以作為金屬箔合金，如含有鎳、鉻、鐵和其他金屬的銅合金使用。導電層也可以是金屬合金，並且典型地經由濺射步驟、然後經由電鍍步驟施加在本發明之聚醯亞胺上。在該等類型的製程中，將金屬種塗層首先濺射到聚合物膜上。最後，經由電鍍或電沈積將較厚的金屬塗層施加在種塗層上。這樣濺射的金屬層也可以在高於聚合物的玻璃化轉變溫度下進行熱壓以增強剝離強度。 As used herein, the terms "conductive layers" and "conductive foils" mean metal layers or foils (thin films having an electrical conductivity of at least 50% that of high-grade copper). composition). The conductive foil is typically a metal foil. The metal foil need not be used as the element in its pure form; it can also be used as a metal foil alloy, such as a copper alloy containing nickel, chromium, iron and other metals. The conductive layer can also be a metal alloy and is typically applied on the polyimide of the invention via a sputtering step followed by an electroplating step. In these types of processes, a metal seed coating is first sputtered onto a polymer film. Finally, a thicker metallic coating is applied over the seed coating via electroplating or electrodeposition. Such sputtered metal layers can also be hot pressed above the glass transition temperature of the polymer to enhance peel strength.

特別合適的金屬基材係軋製退火銅或者軋製退火銅合金的箔。在許多情況下，已證明在塗覆之前預處理金屬基材係有利的。此預處理可以包括但不限於在銅、鋅、鉻、錫、鎳、鈷、其他金屬和該等金屬的合金的薄層的金屬上電沈積或浸漬沈積。預處理可以由化學處理或機械粗糙化處理組成。已經發現，該預處理使聚合物層的黏附以及因此剝離強度能夠進一步增加。除了使表面粗糙化外，化學預處理還可能導致金屬氧化物基團的形成，使金屬與聚醯亞胺層的黏附能夠進一步增加。可以將該預處理施加至金屬的兩側，使在兩側上的與基材的黏附能夠增強。 A particularly suitable metal substrate is a foil of rolled annealed copper or a rolled annealed copper alloy. In many cases it has proven advantageous to pretreat the metal substrate prior to coating. This pretreatment may include, but is not limited to, electrodeposition or immersion deposition on the metal of thin layers of copper, zinc, chromium, tin, nickel, cobalt, other metals, and alloys of these metals. Pretreatment can consist of chemical treatment or mechanical roughening. It has been found that this pretreatment enables a further increase in the adhesion and thus the peel strength of the polymer layer. In addition to roughening the surface, the chemical pretreatment may also lead to the formation of metal oxide groups, enabling a further increase in the adhesion of the metal to the polyimide layer. This pretreatment can be applied to both sides of the metal to enable enhanced adhesion to the substrate on both sides.

在一個實施方式中，金屬包層的層壓物可以包括為多層聚合物膜的製品和黏附至多層膜的第一外層的外表面的第一金屬層。在一個實施方式中，金屬包層的層壓物可以包含黏附至多層膜的第二外層的外表面的第二金屬層。在一個實施方式中，第一金屬層、第二金屬層或者這兩個金屬層可以是銅。在一個實施方式中，本發明之包含雙側銅包層的金屬包層的層壓物可以藉由將銅箔層壓至多層膜的兩側上來製備。 In one embodiment, a metal-clad laminate may include an article that is a multilayer polymer film and a first metal layer adhered to an outer surface of a first outer layer of the multilayer film. In one embodiment, the metal-clad laminate may comprise a second metal layer adhered to the outer surface of the second outer layer of the multilayer film. In one embodiment, the first metal layer, the second metal layer, or both metal layers may be copper. In one embodiment, a metal-clad laminate comprising double-sided copper cladding of the present invention can be prepared by laminating copper foil to both sides of a multilayer film.

應用 application

在一個實施方式中，可以使用具有聚合物膜層的製品用於許多電子裝置應用，如有機電子裝置中。例如，包括裝置基材、觸摸面板、用於濾色器片的基材、覆蓋膜等的層可以在裝置中以多層佈置形成。每個層的具體材料的特性要求係獨特的，並且可以藉由適當選擇每個層的聚合物來解決。可以得益於具有具有多個聚合物膜層的製品的有機電子裝置包括但不限於：(1)將電能轉換為輻射的裝置(例如，發光二極體、發光二極體顯示器、照明裝置、光源、或二極體雷射器)，(2)藉由電子方法檢測信號的裝置(例如，光電檢測器、光導電池、光敏電阻器、光控繼電器、光電電晶體、光電管、IR檢測器、生物感測器)，(3)將輻射轉換為電能的裝置(例如，光伏裝置或太陽能電池)，(4)將一個波長的光轉換成更長波長的光的裝置(例如，下變頻磷光體裝置)；以及(5)包括一個或多個電子部件的裝置，該一個或多個電子部件包括一個或多個有機半導體層(例如，電晶體或二極體)。 In one embodiment, articles having polymeric film layers can be used in many electronic device applications, such as in organic electronic devices. For example, layers including a device substrate, a touch panel, a substrate for a color filter sheet, a cover film, etc. may be formed in a multilayer arrangement in a device. The specific material property requirements of each layer are unique and can be addressed by appropriate selection of polymers for each layer. Organic electronic devices that may benefit from having articles with multiple polymer film layers include, but are not limited to: (1) devices that convert electrical energy into radiation (e.g., light emitting diodes, light emitting diode displays, lighting devices, light sources, or diode lasers), (2) devices that detect signals electronically (for example, photodetectors, photoconductive cells, photoresistors, photorelays, phototransistors, photocells, IR detectors, biosensors), (3) devices that convert radiation into electricity (e.g., photovoltaic devices or solar cells), (4) devices that convert light from one wavelength to longer wavelengths (e.g., down-converting phosphors device); and (5) a device comprising one or more electronic components including one or more organic semiconductor layers (eg, transistors or diodes).

在一個實施方式中，具有多個聚合物膜層的金屬包層的層壓物可以用於柔性印刷連接板，或半導體裝置，或CSP(晶片級封裝)、覆晶薄膜(COF)、COL(引線上晶片)、LOC(晶片上引線)、多晶片模組(「MCM」)、球閘陣列(「BGA」或微球閘陣列)的封裝材料的管芯焊盤鍵合和/或帶式自動鍵合(「TAB」)。 In one embodiment, metal-clad laminates with multiple polymer film layers can be used for flexible printed connection boards, or semiconductor devices, or CSP (wafer level packaging), chip-on-film (COF), COL ( Die pad bonding and/or ribbon bonding of packaging materials for chip on lead), LOC (lead on chip), multi-chip module (“MCM”), ball gate array (“BGA” or microball gate array) Automatic bonding ("TAB").

在另一實施方式中，具有聚合物膜層的製品可用於晶圓級積體電路封裝，在晶圓級積體電路封裝中，使用在具有小於100μm的厚度的導電層(典型地金屬)與含有多個積體電路管芯的晶圓之間***的聚醯亞胺膜製成複合材料。在一個(晶圓級積體電路封裝)實施方式中，藉由導電通路將導電通路與管芯連接，如引線鍵合、導電金屬、焊接凸點等。 In another embodiment, an article having a polymeric film layer can be used in wafer-level integrated circuit packaging in which a conductive layer (typically metal) with a thickness of less than 100 μm is used in combination with Composite material is made of polyimide film interposed between wafers containing multiple integrated circuit dies. In one (WLP) embodiment, the conductive vias are connected to the die by conductive vias, such as wire bonds, conductive metal, solder bumps, and the like.

在一個實施方式中，具有無機基材和聚合物膜層的製品，如玻璃或陶瓷層壓物，可以用作結構或建築應用的抗衝擊層壓物，如抗颶風窗、防盜板和防爆結構。例如，由層壓玻璃構成的玻璃梁通常在所有板層斷裂的情況下提供差的斷裂後堅固性。將無機基材與延展性聚合物層組合的製品可以改善失效後的結構性能並擴大該等層壓物的應用範圍。在一個實施方式中，具有無機基材和聚合物膜層的結構層壓物也可以用作減音層壓物，如隔音板。 In one embodiment, articles having an inorganic substrate and a polymeric film layer, such as glass or ceramic laminates, can be used as impact-resistant laminates for structural or architectural applications, such as hurricane-resistant windows, burglar-proof panels, and blast-proof structures . For example, glass beams constructed of laminated glass typically provide poor post-fracture robustness if all plies fail. Articles combining inorganic substrates with ductile polymer layers can improve post-failure structural performance and expand the range of applications for such laminates. In one embodiment, a structural laminate having an inorganic substrate and a polymeric film layer can also be used as a sound-attenuating laminate, such as an acoustic panel.

在一個實施方式中，具有無機基材和聚合物膜層的製品可以用於抗穿透層壓物的應用，如防彈玻璃和裝甲。例如，防彈玻璃係堅固且光學透明的材料，其特別抵抗射彈的穿透並且可以從多層膜中的聚合物層的更低剛性的特性中受益。在一個實施方式中，陶瓷基材，如單晶藍寶石、氮氧化鋁或其他氮氧化物和尖晶石陶瓷，可以被層壓至聚合物膜層並用作透明裝甲。在一些情況下，該等陶瓷層壓物可以大大減輕裝甲的重量，同時提供與玻璃層壓物相同的抗穿透性。 In one embodiment, an article having an inorganic substrate and a polymeric film layer can be used in penetration resistant laminate applications such as ballistic resistant glass and armor. For example, bulletproof glass is a strong and optically transparent material that is particularly resistant to penetration by projectiles and can benefit from the less rigid nature of the polymer layers in multilayer films. In one embodiment, a ceramic substrate, such as single crystal sapphire, aluminum oxynitride or other oxynitride and spinel ceramics, can be laminated to a polymer film layer and used as a transparent armor. In some cases, such ceramic laminates can greatly reduce the weight of armor while providing the same penetration resistance as glass laminates.

在一個實施方式中，具有無機基材和聚合物膜層的製品可以用於建築應用或運輸應用，在該等應用中希望抗衝擊性、抗穿透性和聲音減弱的組合。例如，車輛上的擋風玻璃可以包含一種或多種無機基材和一個或多個聚合物膜層，它們為擋風玻璃提供所希望的抗衝擊性、抗穿透性和隔音性。 In one embodiment, an article having an inorganic substrate and a polymeric film layer may be used in construction or transportation applications where a combination of impact resistance, penetration resistance, and sound attenuation is desired. For example, a windshield on a vehicle may comprise one or more inorganic substrates and one or more polymeric film layers that provide the windshield with the desired impact resistance, penetration resistance, and sound insulation.

在一個實施方式中，具有無機基材和聚合物膜層的製品可以用作電子設備的面板，如消費電子設備的顯示器。 In one embodiment, an article having an inorganic substrate and a polymeric film layer can be used as a panel for an electronic device, such as a display for a consumer electronic device.

可以藉由參考說明但不限制本發明之以下實例注意到本發明之有利特性。除非另外指明，否則所有份數和百分比皆為按重量計。 The advantageous characteristics of the invention may be noticed by reference to the following examples which illustrate but do not limit the invention. All parts and percentages are by weight unless otherwise indicated.

實例 example

測試方法 Test Methods

CIE L*，a*，b*顏色的測量 Measurement of CIE L*, a*, b* color

顏色測量使用ColorQuest® XE雙光束分光光度計(維吉尼亞州雷斯頓的亨特聯合實驗室有限公司(Hunter Associates Laboratory,Inc.,Reston,VA))，使用D65照明和10度觀察器，在380至780nm波長範圍內以全透射模式進行。百分比霧度和透射率也使用這個儀器測量。 Color measurements were made using a ColorQuest® XE dual-beam spectrophotometer (Hunter Associates Laboratory, Inc., Reston, VA) using D65 illumination and a 10 degree observer , performed in total transmission mode in the wavelength range from 380 to 780 nm. Percent haze and transmittance are also measured using this instrument.

厚度 thickness

膜厚度藉由使用接觸式FISCHERSCOPE MMS PC2模組化測量系統厚度規(康涅狄格州溫莎的飛世爾科技公司(Fisher Technology Inc.,Windsor,CT))測量膜輪廓上的5個位置來確定。 Film thickness was determined by measuring 5 locations on the film profile using a contact FISCHERSCOPE MMS PC2 Modular Measurement System thickness gauge (Fisher Technology Inc., Windsor, CT).

實例1和2以及對比實例1 Examples 1 and 2 and comparative example 1

對於第一聚合物層，將6FDA 1.0//TFMB 0.75/HMD 0.25(莫耳當量)的單體組成、298.2g無水DMAc和50.0g的4,4’-(六氟異亞丙基)二鄰苯二甲酸酐(6FDA，Synasia公司，新澤西州麥塔成市)添加到配備有機械攪拌和氮氣吹掃的氣氛的500-ml反應容器中。在20分鐘的時間段內，緩慢添加25.03g的三氟甲基聯苯胺(TFMB，Seika Corp.,Wakayam Seika Kogyo公司，日本)和3.27g的1,6-二胺基己烷(HMD，奧勒岡州波特蘭的TCI美國公司(TCI America,Portland,OR))。將反應混合物在40℃下攪拌並加熱16小時。溶液變成稍微黏性的。膜藉由在經脫模劑處理的玻璃上刮刀塗覆聚醯胺酸溶液來製備。將聚醯胺酸膜在80℃下乾燥以形成具有大約70wt%至80wt%固體的膜。然後在20分鐘的進程內，將膜在150℃至300℃的烘箱中固化。 For the first polymer layer, a monomer composition of 6FDA 1.0//TFMB 0.75/HMD 0.25 (molar equivalents), 298.2 g of anhydrous DMAc and 50.0 g of 4,4'-(hexafluoroisopropylidene) diortho Phthalic anhydride (6FDA, Synasia Corporation, Metacheng, NJ) was added to a 500-ml reaction vessel equipped with mechanical stirring and a nitrogen-purged atmosphere. Over a period of 20 minutes, 25.03 g of trifluoromethylbenzidine (TFMB, Seika Corp., Wakayam Seika Kogyo Company, Japan) and 3.27 g of 1,6-diaminohexane (HMD, Austria TCI America, Portland, OR). The reaction mixture was stirred and heated at 40 °C for 16 hours. The solution became slightly viscous. Films were prepared by doctor-blading polyamic acid solutions on release-treated glass. The polyamic acid membrane was dried at 80°C to form a membrane with approximately 70 wt% to 80 wt% solids. The film was then cured in an oven at 150°C to 300°C over the course of 20 minutes.

對於第二聚合物層，將BPDA 0.1/6FDA 0.9//TFMB 1.0的單體組成物、15.519kg的TFMB和175.398kg的DMAc添加至氮氣吹掃的80加侖反應器中，同時攪拌。將溶液攪拌至使得TFMB完全溶解在DMAc溶劑中，並在所有後續步驟期間繼續攪拌。對於該程序，將反應混合物加熱至約40℃。經6小時的時間段添加1.398kg的聯苯四甲酸二酐(BPDA，三菱化學公司(Mitsubishi Chemical Co.)，日本)和19.007kg的6FDA。預聚物在25℃下的黏度係約1.5泊。 For the second polymer layer, the monomer composition of BPDA 0.1/6FDA 0.9//TFMB 1.0, 15.519 kg of TFMB and 175.398 kg of DMAc were added to a nitrogen purged 80 gallon reactor while stirring. The solution was stirred until TFMB was completely dissolved in the DMAc solvent, and stirring was continued during all subsequent steps. For this procedure, the reaction mixture was heated to about 40°C. 1.398 kg of biphenyltetracarboxylic dianhydride (BPDA, Mitsubishi Chemical Co., Japan) and 19.007 kg of 6FDA were added over a period of 6 hours. The viscosity of the prepolymer at 25°C is about 1.5 poise.

藉由在氮氣吹掃的反應器中添加6FDA和BPDA粉末在DMAc中的混合物，使聚合物的一部分聚合(「加工(finish)」)至約376.9泊。在40℃下經大約24小時的歷程添加6FDA/BPDA單體使材料聚合。 A portion of the polymer was polymerized ("finished") to about 376.9 poise by adding a mixture of 6FDA and BPDA powders in DMAc in a nitrogen purged reactor. The material was polymerized by addition of 6FDA/BPDA monomer at 40°C over the course of approximately 24 hours.

將147.6kg的該聚合物溶液與2.9kg的25wt%的1,2-二甲基咪唑在DMAc中的溶液和另外的28.6kg的DMAc合併。黏度係500泊。使材料通過20微米的過濾器介質過濾，並在輥到輥製程中澆鑄到3密耳熱穩定化的PET膜上。使用約138℃的峰值溫度驅除溶劑並產生含有一些殘餘DMAc(50wt%-90wt%固體)的生膜。完全去除溶劑之後的乾燥厚度目標將產生2.8密耳的膜。將1.42密耳PET用作保護生膜的表面的覆蓋片。 147.6 kg of this polymer solution were combined with 2.9 kg of a 25 wt% solution of 1,2-dimethylimidazole in DMAc and a further 28.6 kg of DMAc. The viscosity is 500 poise. The material was filtered through 20 micron filter media and cast onto 3 mil heat stabilized PET film in a roll to roll process. A peak temperature of about 138°C was used to drive off the solvent and produce a green film containing some residual DMAc (50 wt% - 90 wt% solids). The dry thickness target after complete solvent removal will yield a 2.8 mil film. 1.42 mil PET was used as a cover sheet to protect the surface of the green film.

將乾膜從帶剝離並且在約110℃至約655℃的溫度(輻射加熱器表面溫度)的拉幅機烘箱中用輻射加熱器加熱以使聚合物膜乾燥並醯亞胺化。 The dry film is peeled from the tape and heated with a radiant heater in a tenter oven at a temperature of about 110°C to about 655°C (radiant heater surface temperature) to dry and imidize the polymer film.

對於對比實例1(CE1)，在該等聚合物膜層的任一層上都不進行矽烷處理。 For Comparative Example 1 (CE1), no silane treatment was performed on any of the polymer film layers.

對於實例1和2(E1-E2)，製備用於預處理聚合物膜的表面的矽烷溶液。將MeOH/H2O(95/5 v/v)添加至3-(2-胺基乙基胺基)丙基三甲氧基矽烷(AEAPTMS)中以形成1wt% AEAPTMS溶液，將其輥壓1-2小時。對於E1，僅 第一聚合物層的表面進行預處理。對於E2，第一聚合物層的表面和第二聚合物層的表面各自進行預處理。 For Examples 1 and 2 (E1-E2), silane solutions used to pretreat the surface of the polymer film were prepared. MeOH/ H2O (95/5 v/v) was added to 3-(2-aminoethylamino)propyltrimethoxysilane (AEAPTMS) to form a 1 wt% AEAPTMS solution, which was rolled for 1 -2 hours. For El, only the surface of the first polymer layer was pretreated. For E2, the surface of the first polymer layer and the surface of the second polymer layer were each pretreated.

聚醯亞胺膜-聚醯亞胺膜層壓 Polyimide film-Polyimide film lamination

對於E1-E2和CE1，以以下方式形成聚合物膜對聚合物膜。將聚醯亞胺膜浸入異丙醇中並允許其在清潔的環境中風乾。使用刮板將每個經處理的樣品塗覆在一側上，並且立即用100%甲醇沖洗過量的預處理溶液。藉由使表面清潔並且不經預處理，對樣品進行塗覆以允許在一個邊緣脫開。使用壓縮空氣蒸發過量的甲醇。之後，將具有所施加的處理的每個膜樣品在熱板上110℃下軟烘烤15分鐘，其中一塊清潔玻璃充當緩衝以保持膜的表面清潔。組裝夾層結構，其包括：金屬板(14”×14”)/增強矽酮橡膠片/金屬板/緩衝聚醯亞胺膜/FEP/樣品(2個聚醯亞胺膜)/FEP/緩衝聚醯亞胺膜/金屬板/增強矽酮橡膠片/金屬板。將夾層裝入15”×15”Wabash壓機(型號GS30H-15-CX，Wabash MPI，沃巴什，伊利諾州)中並關閉壓板。將樣品在真空下加熱預定的時間，允許在壓機中冷卻，並且從壓機中移出。表1列出了每個樣品的溫度、壓力和時間。為了測試黏附，將每個樣品的未處理邊緣用作拉片以手動拉開層壓物。「通過(Pass)」展示層壓物抗分離，而「未通過(Fail)」展示層壓物容易在小阻力的情況下被拉開。 For E1-E2 and CE1, polymer film to polymer film was formed in the following manner. Dip the polyimide membrane in isopropanol and allow to air dry in a clean environment. Each treated sample was coated on one side using a squeegee, and excess pretreatment solution was immediately rinsed with 100% methanol. Samples were coated to allow release at one edge by leaving the surface clean and without pretreatment. Excess methanol was evaporated using compressed air. Afterwards, each film sample with the applied treatment was soft baked on a hot plate at 110° C. for 15 minutes, with a piece of clean glass acting as a buffer to keep the surface of the film clean. Assemble a sandwich structure consisting of: metal plate (14" x 14")/reinforced silicone rubber sheet/metal plate/buffered polyimide film/FEP/sample (2 polyimide films)/FEP/buffered polyimide film Imide film/metal plate/reinforced silicone rubber sheet/metal plate. The sandwich was loaded into a 15" x 15" Wabash press (Model GS30H-15-CX, Wabash MPI, Wabash, IL) and the platens were closed. The samples were heated under vacuum for a predetermined time, allowed to cool in the press, and removed from the press. Table 1 lists the temperature, pressure and time for each sample. To test for adhesion, the untreated edge of each sample was used as a pull tab to manually pull the laminate apart. "Pass" shows that the laminate is resistant to separation, while "Fail" shows that the laminate is easily pulled apart with little resistance.

Figure 111133737-A0202-12-0042-1
Figure 111133737-A0202-12-0042-1

使用掃描XPS微探針(PHI Quantera，Physical Electronics,Inc.，查哈森，明尼蘇達州)進行X射線光電子能譜(XPS)分析。首先藉由寬測量掃描檢查每個樣品表面以確定表面上存在什麼元素。獲取高解析度光譜以確定所檢測的元素的化學狀態以及它們的原子濃度。XPS儀器處於基礎壓力小於約5×10-10托的超高真空下，並且用單色Al X射線源操作。所有實驗均以45°出口角進行，分析面積在200μm×200μm。使用半球形分析儀收集光電子。使用PHI MultiPak@軟體版本9.3用於數據分析。 X-ray photoelectron spectroscopy (XPS) analysis was performed using a scanning XPS microprobe (PHI Quantera, Physical Electronics, Inc., Chahassen, Minnesota). Each sample surface is first inspected by a wide measurement scan to determine what elements are present on the surface. Acquire high-resolution spectra to determine the chemical state of the detected elements as well as their atomic concentrations. The XPS instrument is under ultra-high vacuum with a base pressure of less than about 5 x 10 -10 Torr and operates with a monochromatic Al X-ray source. All experiments were performed with an exit angle of 45° and the analysis area was 200 μm × 200 μm. Photoelectrons were collected using a hemispherical analyzer. PHI MultiPak@ software version 9.3 was used for data analysis.

對於對比實例2(CE2)，對如以上所描述的第一和第二聚合物膜層兩者都進行預處理和軟烘烤，但不層壓在一起。表2總結了剝離該等層壓膜之後所產生的介面表面的XPS數據，以原子百分比計。與未處理的表面相比，矽烷處理的表面示出存在Si和更高的N/F比例。對於E1，矽烷看起來在剝離之後主要留在經處理的第一聚合物層上。對於E2，在預處理兩個聚合物膜層的情況下，剝離之後矽烷從介面存在於兩個表面上。在該等實例中，在兩個表面上都存在Si表明正被檢查的表面確實係這兩個層之間的介面。 For Comparative Example 2 (CE2), both the first and second polymer film layers as described above were pretreated and soft baked, but not laminated together. Table 2 summarizes the XPS data, in atomic percent, of the resulting interface surfaces after peeling off the laminated films. The silane-treated surface showed the presence of Si and a higher N/F ratio compared to the untreated surface. For El, the silane appears to remain mainly on the treated first polymer layer after exfoliation. For E2, in the case of pretreatment of the two polymer film layers, silane is present on both surfaces from the interface after exfoliation. In these examples, the presence of Si on both surfaces indicates that the surface being inspected is indeed the interface between these two layers.

Figure 111133737-A0202-12-0043-2
Figure 111133737-A0202-12-0043-2

使用配備有30keV Bi原離子束和用於電荷中和的脈衝泛射式電子槍的TOF-SIMS M6(德國明斯特的艾飛拓科技公司(IONTOF GmbH,Muenster,Germany))進行TOF-SIMS表面光譜分析。分析面積被限制為500×500μm2，同時維持1012個離子/cm2或更小的原離子劑量密度以確保靜態SIMS條件(2nm的探針深度)。 TOF-SIMS surfaces were performed using a TOF-SIMS M6 (IONTOF GmbH, Muenster, Germany) equipped with a 30keV Bi primary ion beam and a pulsed flood electron gun for charge neutralization spectral analysis. The analysis area was limited to 500×500 μm 2 while maintaining a primary ion dose density of 10 12 ions/cm 2 or less to ensure static SIMS conditions (probe depth of 2 nm).

特別地，經預處理的聚合物層示出相對更高的CN-物質的表面含量。所關注的二次離子(CN-)的峰面積藉由代表基質材料的特徵峰歸一化。對於聚醯亞胺膜，可以使用碎片離子峰、分子離子峰或烴峰，如C3N-、C7 -、CF3 -、C7H4NO-。可以計算來自相似樣品的相對峰面積比來比較相關物質的相對量。當在層壓之前用胺試劑處理聚合物膜層時，該等經預處理的層的歸一化峰面積比對於CN-相關物質示出大於10%的增加。這可以歸因於在介面處形成了另外的C-N鍵和/或具有醯胺官能基的物質。 In particular, the pretreated polymer layer shows a relatively higher surface content of CN - species. The peak area of the secondary ion of interest (CN − ) was normalized by the characteristic peak representing the matrix material. For polyimide membranes, fragment ion peaks, molecular ion peaks or hydrocarbon peaks, such as C 3 N − , C 7 − , CF 3 − , C 7 H 4 NO − , can be used. Relative peak area ratios from similar samples can be calculated to compare relative amounts of related species. When the polymer film layers were treated with amine reagents prior to lamination, the normalized peak area ratios of the pretreated layers showed a greater than 10% increase for CN - related species. This can be attributed to the formation of additional CN bonds and/or species with amide functional groups at the interface.

Figure 111133737-A0202-12-0044-4
Figure 111133737-A0202-12-0044-4

Figure 111133737-A0202-12-0044-3
Figure 111133737-A0202-12-0044-3

應注意的是，並不是所有的以上在一般性描述中所描述的活動皆為必需的，一部分具體活動可能不是必需的，並且除了所描述的那些以外，還可 以進行其他活動。此外，列舉每一個活動的順序不必是它們實施的順序。在閱讀本說明書之後，熟練的所屬技術領域具有通常知識者將能夠確定哪些活動可用於他們具體的需求或期望。 It should be noted that not all of the activities described above in the general description are required, that some specific activities may not be required, and that in addition to those described, for other activities. Furthermore, the order in which each activity is listed is not necessarily the order in which they were performed. After reading this specification, skilled artisans of ordinary knowledge will be able to determine which activities are available for their specific needs or desires.

在前述說明書中，已參考具體實施方式描述了本發明。然而，熟悉該項技術者理解，在不脫離以下請求項中所規定的本發明範圍的情況下可作出各種修改和改變。本說明書中揭露的所有特徵可以由服務於相同、等同或類似目的替代特徵來代替。因此，應該在說明性的而非限制性的意義上看待本說明書，並且所有此類修改均旨在包括在本發明之範圍內。 In the foregoing specification, the invention has been described with reference to specific embodiments. However, those skilled in the art appreciate that various modifications and changes can be made without departing from the scope of the present invention as defined in the claims below. All features disclosed in this specification may be replaced by alternative features serving the same, equivalent or similar purpose. Accordingly, the specification should be regarded in an illustrative rather than a restrictive sense, and all such modifications are intended to be included within the scope of present invention.

上面已經關於具體實施方式描述了益處、其他優點和問題的解決方案。然而，益處、優點、問題的解決方案、以及可能引起任何益處、優點、或解決方案出現或使其變得更明顯的一個或多個任何要素不會被解釋為任何或所有請求項的關鍵的、必要的或基本的特徵或要素。 Benefits, other advantages, and solutions to problems have been described above with respect to specific embodiments. However, benefits, advantages, solutions to problems, and any element or elements that may cause or make apparent any benefits, advantages, or solutions are not to be construed as essential to any or all of the claimed items , essential or essential feature or element.

Claims (22)

一種製品，其包含： An article of manufacture comprising: 第一聚合物膜層，其包括包含第一醯亞胺基團的第一聚合物；以及 a first polymer film layer comprising a first polymer comprising a first imide group; and 第二聚合物膜層，其包括包含第二醯亞胺基團的第二聚合物，其中，在該等層之間的介面處分離該第一和第二聚合物膜層以暴露該第一聚合物膜層的第一介面表面和該第二聚合物膜層的第二介面表面之後： A second polymer film layer comprising a second polymer comprising a second imide group, wherein the first and second polymer film layers are separated at the interface between the layers to expose the first After the first interface surface of the polymer film layer and the second interface surface of the second polymer film layer: (a)使用負二次離子質譜法測量的該第一介面表面處的CN-對C3N-物質的比例相較其在該第一聚合物膜層的本體中的比例高至少10%； (a) the ratio of CN - to C 3 N - species at the surface of the first interface measured using negative secondary ion mass spectrometry is at least 10% higher than its ratio in the bulk of the first polymer film layer; (b)使用負二次離子質譜法測量的該第二介面表面處的CN-對C3N-物質的比例相較其在該第二聚合物膜層的本體中的比例高至少10%；或者 (b) the ratio of CN - to C 3 N - species at the surface of the second interface measured using negative secondary ion mass spectrometry is at least 10% higher than its ratio in the bulk of the second polymer film layer; or (c)使用負二次離子質譜法測量的該第一介面表面處的CN-對C3N-物質的比例相較其在該第一聚合物膜層的本體中的比例高至少10%，並且以負二次離子質譜法測量的該第二介面表面處的CN-對C3N-物質的比例相較其在該第二聚合物膜層的本體中的比例高至少10%。 (c) the proportion of CN - to C 3 N - species at the surface of the first interface measured using negative secondary ion mass spectrometry is at least 10% higher than its proportion in the bulk of the first polymer film layer, And the ratio of CN − to C 3 N − species at the surface of the second interface measured by negative secondary ion mass spectrometry is at least 10% higher than that in the bulk of the second polymer film layer. 如請求項1所述之製品，其中，包含醯亞胺基團的該第一和第二聚合物各自單獨地選自由以下組成之群組：聚醯亞胺、聚(醯胺-醯亞胺)、聚(醚-醯亞胺)、聚(酯-醯亞胺)、包含醯胺、酯或醚基團的共聚物、及其混合物。 The article of claim 1, wherein the first and second polymers comprising imide groups are each independently selected from the group consisting of polyimides, poly(amide-imides) ), poly(ether-imides), poly(ester-imides), copolymers comprising amide, ester or ether groups, and mixtures thereof. 如請求項2所述之製品，其中，該聚醯亞胺衍生自二酐、氟化的芳香族二胺和脂肪族二胺。 The article of claim 2, wherein the polyimide is derived from dianhydrides, fluorinated aromatic diamines, and aliphatic diamines. 如請求項3所述之製品，其中，該二酐包含脂環族二酐。 The product according to claim 3, wherein the dianhydride comprises alicyclic dianhydride. 如請求項1所述之製品，其中： The product as described in Claim 1, wherein: (a)該第一聚合物膜層具有300℃或更低的Tg； (a) the first polymer film layer has a Tg of 300°C or less; (b)該第二聚合物膜層具有300℃或更低的Tg；或者 (b) the second polymer film layer has a Tg of 300°C or less; or (c)該第一和第二聚合物膜層兩者都具有300℃或更低的Tg。 (c) Both the first and second polymer film layers have a Tg of 300°C or less. 如請求項1所述之製品，其中，當使用由ASTM E313描述的程序在25μm的厚度下測量時，該製品具有1.25或更小的b*和2.25或更小的黃度指數。 The article of claim 1, wherein the article has a b* of 1.25 or less and a yellowness index of 2.25 or less when measured at a thickness of 25 μm using the procedure described by ASTM E313. 如請求項1所述之製品，其中，當在25μm的厚度下測量時，該製品具有15%或更小的霧度和93或更大的L*。 The article of claim 1, wherein the article has a haze of 15% or less and an L* of 93 or more when measured at a thickness of 25 μm. 如請求項1所述之製品，其進一步包含在與該第二聚合物膜層相反的一側上與該第一聚合物膜層接觸的無機基材。 The article of claim 1, further comprising an inorganic substrate in contact with the first polymer film layer on a side opposite to the second polymer film layer. 一種抗衝擊製品，其包含如請求項1所述之製品。 An impact-resistant article, which includes the article as described in claim 1. 一種抗穿透製品，其包含如請求項1所述之製品。 An anti-penetration product comprising the product as described in claim 1. 一種減音製品，其包含如請求項1所述之製品。 A sound-reducing product, which includes the product described in claim 1. 一種金屬包層的層壓物，其包含如請求項1所述之製品。 A metal-clad laminate comprising the article of claim 1. 一種用於形成製品之方法，其中，該製品包含： A method for forming an article, wherein the article comprises: 第一聚合物膜層，其包含具有第一玻璃化轉變溫度並包含第一醯亞胺基團的第一聚合物；以及 a first polymer film layer comprising a first polymer having a first glass transition temperature and comprising a first imide group; and 第二聚合物膜層，其包含具有第二玻璃化轉變溫度並包含第二醯亞胺基團的第二聚合物，其中，該第一玻璃化轉變溫度等於或低於該第二玻璃化轉變溫度，並且該方法包括： A second polymer film layer comprising a second polymer having a second glass transition temperature and comprising a second imide group, wherein the first glass transition temperature is equal to or lower than the second glass transition temperature temperature, and the method includes: (a)將胺試劑施加至該第一聚合物膜層的表面、該第二聚合物膜層的表面、或兩者； (a) applying an amine reagent to the surface of the first polymer film layer, the surface of the second polymer film layer, or both; (b)使該等聚合物膜層接觸，使得具有胺試劑的表面在該等聚合物膜層之間的介面處；以及 (b) contacting the polymer film layers such that the surface with the amine reagent is at the interface between the polymer film layers; and (c)向該製品施加熱量和壓力。 (c) applying heat and pressure to the article. 如請求項13所述之方法，其中，該胺試劑選自由一級胺、二級胺、或其混合物組成之群組。 The method according to claim 13, wherein the amine reagent is selected from the group consisting of primary amines, secondary amines, or mixtures thereof. 如請求項13所述之方法，其中，該胺試劑包含多胺。 The method according to claim 13, wherein the amine reagent comprises polyamine. 如請求項13所述之方法，其中，該胺試劑包括包含水解的低聚物的金屬醇鹽。 The method of claim 13, wherein the amine reagent comprises a metal alkoxide comprising a hydrolyzed oligomer. 如請求項13所述之方法，其中，施加至該第一聚合物膜層的表面的該胺試劑與施加至該第二聚合物膜層的表面的該胺試劑相同或不同。 The method of claim 13, wherein the amine reagent applied to the surface of the first polymer film layer is the same or different from the amine reagent applied to the surface of the second polymer film layer. 如請求項13所述之方法，其中，熱量係在該第一聚合物的該玻璃化轉變溫度之低20度至高50度範圍內的溫度。 The method of claim 13, wherein heat is at a temperature ranging from 20 degrees lower to 50 degrees higher than the glass transition temperature of the first polymer. 如請求項13所述之方法，其中，該胺試劑包含已被鈍化並且可以藉由施加熱量而被熱活化的胺基團。 The method of claim 13, wherein the amine reagent comprises an amine group that has been deactivated and can be thermally activated by applying heat. 如請求項19所述之方法，其中，該已被鈍化的胺基團在活化後還可以交聯該第一聚合物、該第二聚合物、或兩者。 The method of claim 19, wherein the deactivated amine group can also cross-link the first polymer, the second polymer, or both after activation. 如請求項13所述之方法，其中，在將該胺試劑施加至一個或兩個聚合物膜層的表面之前，該一個或兩個聚合物膜層的表面經歷電暈處理或電漿處理。 The method of claim 13, wherein the surface of the one or both polymer film layers undergoes corona treatment or plasma treatment before applying the amine reagent to the surface of the one or both polymer film layers. 如請求項13所述之方法，其中： The method as described in claim 13, wherein: 該製品進一步包含在與該第二聚合物膜層相反的一側上與該第一聚合物膜層接觸的無機基材； The article further comprises an inorganic substrate in contact with the first polymer film layer on a side opposite the second polymer film layer; 在步驟(a)期間，還將胺試劑施加至該第一聚合物膜層的另一表面、該無機基材的表面、或兩者；以及 During step (a), an amine reagent is also applied to the other surface of the first polymer film layer, the surface of the inorganic substrate, or both; and 在步驟(b)期間，使該第一聚合物膜層與該無機基材接觸，使得具有胺試劑的表面位於該第一聚合物膜層與該無機基材之間的介面處。 During step (b), the first polymer film layer is contacted with the inorganic substrate such that the surface with the amine reagent is at the interface between the first polymer film layer and the inorganic substrate.
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